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Ashe ~ She's a Carry for a reason.
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Granted; this is my first, but I use this build often and it never disappoints.
If you use her right she can be a pain for harassment as the beginning. ;)
I hope you find this as useful as I do.
Boots of Swiftness are probably your best bet, as it'll give you the most efficient speed to give off another quick arrow. You may get away with Beserker's Grieves, but that's your funeral.
A Phantom Dancer after the Edge will give you the sufficient speed and crit* to efficiently farm minions for that extra money and exp and ward off any close combaters. (Works great against Tryndamere)
Black Cleaver. Well.. What's better than rubbing salt in an open wound? So if it gets to the point where you're owning face grab the good 'ol Black Cleaver. :D
Guardian Angel This would be the most effective armor for a revive just in case you didn't quit kill him the first time, or if you need to get away.
Now these next two items can be inter-changed; depending on your situation.
Frozen Heart - This provides the great defense and ability cooldowns to help out with the kill.
Force of Nature is great when needing some magic resist, as not only does it give great, but it also provides you with health regen which will make you more sustainable in battle.
Options for the #2 spell
Ignite - I never normally choose ignite, because I usually play with a Teemo who's darts are poisoned 24/7 anyway. But this could be useful to stop Gankers from getting away, or the dreaded Undying Rage.
Cleanse - This can be a life saver. Literally. If you're in the heat of a team battle and they focus you and your exhausted/stunned/slowed; Cleanse will be the perfect spell to ensure your safety.
Revive - This spell would only be good if there's a possibility your team may not do that great. Because it kind of sucks when you think you're going to win, but they somehow pull an ace and you're dead for 55 seconds. Yeah not pretty hm?
Heal - Only cool kids use heal. Need I say more? It does exactly what it says... Heal. :D
Clarity - I tend to pick this sometimes when I'm playing as Ashe can be very mana dependent at the beginning. And it also sucks when you're half way through a game and a Malphite is running to base with 100 health and you have no mana for Enchanted Arrow. -_-
Those would be the only "appropriate" 2nd spells to use.
Now hopefully when you reach your Phantom Dancer you'll be able to effectively use Volley to snare those multiple minion kills. :)