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Overmelding is the act of putting more materia on a piece of gear than it actually has slots for. This requires a bit of luck to succeed and the requisite crafter level (you can always ask crafters for help).
Note though that this can only be done with craftable gear.
XII can be used for the slots that already exist on gear, and for the first overmeld. Beyond that, you need XI.
If you aren't using crafted gear then it's safe to ignore (or possibly sell) your XI materia.