Build Guide by The Ground Below
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Ability Sequence
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Masteries
Introduction
Hello and welcome to my 
Annie Guide. There is something very mean about an AOE stun and high damage on champion that is hard to kill. Annie is pretty easy to use. The only thing that is difficult about her is timing your stuns, so I have include a section on that. Beyond this, play a few games and you will get to know what you can and cannot do.
I think that the item guide here is right; this gives plenty of damage and enough survivability. Personally I think that any time a guide gives items for all six slots this is a mistake; many of those items will be incorrect for a given game.
In any case I hope that you will find this take on Annie useful.
Masteries
I like nine points in offense for obvious reasons. The nine in offense are probably the best for a DPS caster.
Beyond this we need to address the issue of squishiness. I find that a nice way of doing this is 21 points in defense.
Runes
Annie has pretty short cooldowns, so I go with AP glyphs. Beyond that the Runes are pretty standard for a caster.
Greater Mark of Magic Penetration and 
Greater Quintessence of Magic Penetration offer a lot of Magic Penetration. This is great for a damage Caster.
Greater Seal of Scaling Mana Regeneration and Greater Seal of Replenishment give you plenty of mana. I hate running out of Mana. I have a split of flat and per level mana regeneration to keep you in mana at lower levels; I have been testing mana runes since the nerf and this seems to be the best so far.
Greater Glyph of Scaling Ability Power gives AP and Annie needs AP. AP makes facemelting easier. The other option is 
Greater Seal of Cooldown Reduction is good too, I have been using these to try them. I like them, still not quite sure which is better. More testing is required. The CDR runes work better with Pyromania but at the expense of burst damage. The CDR runes let you throw more spells in teamfights, but a CDR item does that as well.
Summoner Spells
I have been taking 
Clarity with Annie lately. This is much better if you want to get kills solo-laning, but it is not as necessary in the side lanes. If you know you are not going to have a solo (solos are great, btw) you can take 
Teleport or 
Ignite and the associated mastery if you wish.
Ghost gives a much-needed chasing and escape mechanism. This is also one of my favorite summoner spells.
Teleport is a good spell too, but I haven't been taking it as much lately.
Ignite is a good choice too. If 
Vladimir or maybe 
Tryndamere is free this week then I suggest taking this.
Items
I really like 
Rod of Ages. We rush it here so we get our stacks nice and early. It also further counteracts Annie's fragile nature (she is only five after all).
Next comes the 
Sorcerer's Shoes, no surprise there. 
Ionian Boots of Lucidity and 
Mercury's Treads are an option as well.
Next comes the 
Rabadon's Deathcap. This gives you lots of AP; Annie needs lots of AP. Basically we make sure we don't die, then we make sure the opponent does.
From here I really consider the rest of the build situational.
The best defensive items are probably 
Banshee's Veil, 
Frozen Heart and 
Guardian Angel. If you are facing an all-physical (or nearly) a 
Thornmail is a must of course.
Rylai's Crystal Scepter is a kind of hybrid Offensive/defensive item, but in general I find that Pyromania is enough. Basically Rylai's is good, but not great.
On the offensive side, Lich's Bane, 
Void Staff, Deathfire's Grasp and 
Will of the Ancients. If you are having trouble deciding what to get, buy a [Hextech Revolver and reevaluate the situation the next time you are at the shop. If there is a tank that you just can't seem to kill, Void staff is good, but for general damage output I recommend Lich's Bane and Deathfire's Grasp.
Now that 
Morello's Evil Tome exists it is an option as well.
Skill Sequence
Your Disintegrate does lots of damage and has nice range, so we take it first. I find that a point in Molten Shield early helps a lot; it lets you manipulate you Pyromania stacks and harass more aggressively, especially solo laning. A point in Incinerate to get more damage comes next. From here we go burst damage, so we take Disintegrate, then Incinerate.
Manipulating Pyromania
This section primarily covers techniques for manipulating Annie's passive.
You want to have be have 5 Pyromania stacks for the start of every teamfight. This is not to say you should never cast when you have five stacks, just know what you have to do to be back at five by the next major confrontation. Then you want to Tibbers-stun as many of them as you can and proceed to melt enemy faces.
Farming with Incinerate is often too good to pass up. The cooldown is short enough that you can hit, say, the minions on top lane near your base, wolves, mid minions and wraiths. Then start the next teamfight with your shield and you have a Summon: Tibbers-stun ready. This is an example.
Since Incinerate dies not require a target, you can use it to get Pyromania stacks before a fight.
Basically Annie is easy to play once you know how to control the flow of her spells. This just takes conscious effort and practice. Work toward mastery.
Count your spells in team fights. If you can Tibbers stun at the beginning and hit another Incinerate-stun later this is great. You have plenty of mana to spam your spells.
Team Work
You are a DPS caster; in teamfights stand where you won't get hit until the fight starts. There are two ways a fight can start.
Ideally your tank will initiate, then you Summon: Tibbers-stun the enemy carries after a couple seconds (you should know not to bite the tank's heels; if you didn't know you do now). Then focus Disintegrate and Incinerate on their squishy, maybe autoattack a time or two. Then get out until your spells are available again (a second or so). Basically you are taking this time to reposition yourself for more damage and survivability. This is not neseccary if yo are really fed and tanky.
The other option is Summon: Tibbers-stun, then the tank comes in. This is less good but happens with scaredy-tanks. You are built to be able to be durable with health and your shield.
There is a time when you want to have 4 stacks on Pyromania: if the enemy carry is fed and has a banshee's veil, you should pop it with a Disintegrate then stun several enemies with Summon: Tibbers. This reduces your burst but you have to do it, so whatever. Sometimes you can agree with your support or tank to have them pop the viel, which is great. Ashe's auto-attacks with Frostshot active also pop the Veil, I think. 
Cho'Gath 
Ruptures or 
Malphite 
Seismic Shards work too.
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