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The only multi-hit move Heracross can learn is Fury Attack(which doesn't see much competitive use and is a weak non-STAB move). Is there any other move it can learn and put it's ability to use with (like Pin Missile)?

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Yea, pin missile for starters -mandatory eye roll-

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New moves as of X and Y:

-Pin Missile (Level 31)
-Bullet Seed (Level 1)
-Arm Thrust (Level 1)
-Rock Blast (Egg move)

All of these are new moves which take advantage of Skill Link. Pin Missile is better than Megahorn as it is now effectively 125 base power with 95% accuracy. Rock blast is the same, and allows it to crush Flying/Fire types. Bullet Seed is useful for bulky water types (Azumarril, Jellicent and co) and Arm Thrust is usually inferior to Close Combat, unless you don't like the Defence and Special Defence drop.

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Thanks :)