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Below is a guide on how to get some of the rarer Materia in Final Fantasy 7, it is found in special caves called 'Materia Caves', although to access these caves you need to breed special Chocobos.
Quadra Magic Cave
Found just east of the Chocobo Ranch, you will need either a Blue or a Green Chocobo to access this cave.
HP <-> MP Cave
Head just north from the base of Mount Corel, search this area with a Green Chocobo and you should find the HP <-> MP Materia Cave.
Mimic Cave
The Mimic Materia Cave can be found on the island of Wutai, to get to the cave you must first have bred a Green Chocobo.
Knights of the Round Cave
Go to the very North East of the Map and you should find an island called 'The Round Island' quite appropriately named if I do say so myself. The cave is on The Round Island but you need to have bred a Gold Chocobo to get there.