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I wanna be able to get a Sylveon as soon as possible, and having Charm as an egg move solves that problem. In ORAS by the way.

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Yes. In fact, Eevee itself learns Charm at level 29, so you could get a male Eevee of that level and breed it with a female one, and all the offspring with hatch knowing Charm.
Pokemon in the field egg group other than Eevee that also learn Charm by level up are Buneary, Cubchoo, Dedenne, Deerling, Furfrou, Glameow, Snubbull, Meowstic, Minccino, Pachirisu, Phanpy, Skitty, and Teddiursa.

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Thanks KRLW890! I'll do Charm as an Egg move so I can get Sylveon at level 2.
Would breeding a male ditto with Charm and a Ditto work the same way(100% chance of a Charm Eevee?)
If you mean a male Eevee with Charm and Ditto, then yes, that would also work. In fact, I believe Gen 6 was the first gen that allowed females to pass down egg moves as well, so the Eevee could be male or female.
Thanks!