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In Final Fantasy 7 Vincent Valentine is an unlockable character, to unlock Vincent Valentine you must go to ShinRa Mansion in Nibelheim. On the second floor you should find a safe, the code for this same is: Right 37 - Left 10 - Right 59 - Right 97, you must go the direction of stated before the number or the code will not work. If you've done this correctly you should fight the boss battle 'Lost Number', the boss itself shouldn't be to hard so now on to the next step.
After beating Lost Number you should get the Basement Key item, after getting this go down into the basement and just before the libray you should find a door, go through the door and Press X on the Coffin.
Vincent will emerge from the coffin and speak to you about Sephiroth, after that he will return to the coffin, speak to him again then attempt to leave the basement. Vincent will approach you and join your party!