Not Updated For Current Season
The masteries shown here are not yet updated for the current season, the guide author needs to set up the new masteries. As such, they will be different than the masteries you see in-game.
Vayne, the Night Hunter
The world is not always as civilized as people might think. There are still those who would follow the blackest paths of magic and become corrupted by the darker powers that flow through Runeterra. Shauna Vayne knows this fact well. As a young privileged girl in the heart of Demacia's elite, her father tried to convince her of the constabulary's ever-vigilant eye. Young and nave, she truly believed that her world was one of perfect safety, until one night, when a twisted witch took interest in her father. The malevolent woman overcame her father's conciliar guard, then tortured her family before murdering them. The young Shauna escaped only by hiding herself and then fleeing once the hag had departed, plagued by the screams of her loved ones as she ran. A burning hatred was born in her that day, one that could never be denied.
Vayne was able to take care of herself using her father's money, and she began to train as soon as an instructor would have her as a student. By the time she was a fully grown woman, she had become a grim warrior. However, the fields of battle were not to be her home. Demacia needed a protector, one who hunted those lost to the darkness. Shauna used her family's contacts to become the first Night Hunter, and now her prowess is the stuff of legends. It is said that those who practice the black arts quake when they hear that the Night Hunter is on the prowl. Despite her crusade, Shauna has looked at the League of Legends in horror. There are champions who have clearly lost themselves to the blackest of magics, and who have been embraced within the League even though they should be put down for the safety of all. The time has come for the Night Hunter to execute her secret mission to purge the League of Legends.
Not all shadows are to be feared. At least, if Vayne has her way.
This is a guide for a method of playing Vayne which I've found works quite well. It allows you to put out great damage while being able to survive very well due to focusing on dealing damage through Madred's Bloodrazer and Silver Bolts.
Pros / Cons
+ Great damage
+ Great ganker
- Squishy until mid-late game
The CORE item build would be Mercury's Treads and Madred's Bloodrazer. Phantom Dancer and Wit's End should be somewhat included in there. The reasoning for Phantom Dancer and Wit's End is the attack speed. With this build, you aren't going for pure AD. Your method of dealing damage will be percentage based damage from Madred's and your Silver Bolts. If you want to deal more damage through Madred's and Silver Bolts, then you need attack speed. Why not get other attack speed items instead? You could, but I prefer Phantom Dancer for the movement speed and Wit's End for its added magic damage and magic resist. The main thing you're going for with aside from attack speed is survivability, so the magic resist from Wit's End makes it quite desirable for this build.
After obtaining those four items, or possibly before depending on the circumstances, you will want survivability. This is where Guardian's Angel comes in. Armor, magic resist, and a second life all in one great item. After Guardian's Angel you will have to judge the situation and determine what your last item will be. If they have a heavy magic damage team, then get a Force of Nature. If they have a lot of physical damage, go for Randuin's Omen. If they have a balanced team then you may want to go for a Warmog's.
If you should ever complete your item build, then it should go without saying that you buy elixirs.
Trinity Force is a viable alternative that I would probably use in place of Wit's End; however, this build focuses on dealing damage through Silver Bolts and Madred's Bloodrazer, so the double damage proc from Trinity Force wouldn't be much of a bonus seeing as how you will not have great AD. The fact that you can Tumble very often and the fact that Tumble resets your attack timer does make this viable, though.
All rune choices are pretty much up to personal preference. These are what I've found work best for me.
The Quintessences I've chosen are movement speed quints. I've recently taken a liking to using movement speed quints in conjunction with the movement speed mastery. With only Boots of Speed you'll end up with about 380 movement speed because of those two, instead of the normal ~350. This synergizes well with your passive which adds 40 movement speed when facing toward an enemy.
Armor Pen marks for a bit more damage early on in the game even though you're not primarily focusing on AD with this build. It may be wise to swap these for Attack Speed marks which will help later on once you've started picking up a bit more AS elsewhere.
Dodge seals are good for use with the Dodge masteries. Getting a dodge and having increased movement speed is always nice. MP5 or anything like that aren't needed because mana is only an issue in the first few levels, so conserve during that time! Then again, with this build you'll be maxing Silver Bolts first so you won't be spamming Tumble every 2 seconds as opposed to 6 or so.
Flat Magic Resist glyphs for more staying power against those pesky casters during the early laning phases. An alternative could be Magic Resist/level for better scaling into late game in terms of defense, though since you'll be focusing on defensive items in late game, it would probably be wiser to use Flat Magic Resist.
Up to personal preference. I opt to go 15/15 for the added health and dodge bonuses of the defensive tree while still picking up the movement speed and experience boost masteries in utility.
It could prove worth while to delve into the offensive tree for the attack speed mastery or the magic pen mastery(for Madred's, since it will be a good portion of your damage).
First skill you should get AND max out is Silver Bolts. It is great because it deals TRUE damage, meaning if you're fighting an Alistar and he uses his ultimate, he will still die because true damage is not reduced by his ultimate at all. One level of Tumble is perfectly fine for early laning.
After maxing out Silver Bolts, max Tumble, although, you should take one level of Condemn at level 4 because the stun is [obviously] really nice. It's also great for shooting someone who is chasing you away.
Take a level in your ultimate whenever it's available.
Like most other things, these are up to preference.
My main choices would be Ghost and Flash/Ignite. Possible alternatives would be Exhaust, Teleport, or even Clairvoyance(it's a big plus if someone else doesn't have it).
My reasoning for Clairvoyance is that not only does your passive Night Hunter ability not work if you don't have sight of an enemy, but you'll be able to hit them through Brush and the chances of them getting away by trying to juke through it are non-existent.