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But just one time.
Plus you have to have it all physically in your inventory.
Be sure to look that up, because there are a few enemy skills that you will only get (at least) one chance to get.
If you miss it, then kiss that achievement goodbye.
All of these need to be mastered, except for Enemy Skill and Underwater.
Underwater you simply need to own. Enemy Skill you must have learned all skills on one materia.
Best way to master all materia AND have a full Master set, is to defeat Emerald weapon. So basically, remember NOT to blend your materia to get sets with Bugenhaagen, or you'll be mastering them all again!
Honestly, for those who are going for a perfect game, just remember that the Earth Harp and Desert Rose are unique items, whereas for master materia, you can make as much as you want, although time consuming.