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Spells:
Ghost
Flash
Ability Order
Night Hunter (PASSIVE)
Vayne Passive Ability
Intro
Ideal Vayne build especially for tank killing. Purchase Doran's Blade first for the extra health and damage early game. Berserker's Greaves next, then rush Phantom Dancer. By now you should notice a large damage burst. After Dancer get Madred's Bloodrazor for the extra damage in between silver bolts, (also gets that 3rd hit to be pretty damage heavy). Then you want to buy either Wit's End if they have heavy AP, or Sword of the divine if there isn't. Up next is Black Cleaver. Now this makes you hit consecutively harder and harder and it makes it even better once you sell your Doran's Blade and get Bloodthirster for a bit of survivability and a lot of damage output.
Pretty straight forward Ranged AD masteries apply here. 3 points in Deadliness, one point in Archmage's Savvy (helps a tad for tumble). Obviously 4 points into Aclarity for as much early on attack speed that you can get. 3 points in Sorcery helps for her long cooldown for tumble early on. 3 points in Sunder, 3 points in Brute force, and 3 points in Lethality. Reason? Isn't it obvious? Then that 21st point into offense for Havoc. As for the other 9, I put them into utility. 3 points into Preserverence, it helps her stay in lane a little bit better. A point into Haste for the extra speed for running away, or even catching up to someone really fast. I like to put 4 points into awareness for fast level gain. And last point goes into Utility Mastery.
I like to use Ghost and Flash when using Vayne. Both mostly as a defense to run away, but are both usefull offensive spells as well. Other options... maybe exhaust or ignite in place of Ghost, but I believe that Flash is a must. If you do use something other than ghost then put a mastery point into Good Hands instead of Haste.
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