Barret Wallace

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In battle, Barret is one of the strongest in the game.  He's a decent magic user, he's a strong physical attacker, and his Limit Breaks rock.  He also has several Long-range weapons, which allows you to put him in the back ranks without his attack damage suffering, which equals less damage for Barret.  That's always good.  Avoid loading him down with lots of stat-reducing materia however,  It can cut down on his two strongest attributes, his attack and HP.

Limit Breaks
Level 1
Big Shot:  Shoots a fireball thingy from Barret's gun, which gives lots of damage.
Mindblow:  Shoots a blue fireball at the enemy, which empties out it's MP.  While this may not seem worth it, getting rid of your opponents MP is often a real advantage, especially against bosses.

Level 2
Grenade Bomb:  Throws a grenade into the enemies.  Usually the better of the two Level 2 limit breaks, as it hits all enemies and works against bosses.
Hammerblow:  Barret punches an enemy really, really hard, and launches them miles.  This will completely remove an enemy from combat, though it doesn't work against bosses.  Use this only against a strong non-boss single enemy.

Level 3
Satellite Beam:  Has several beams of light from the sky come down and hit the enemies.  Ooh, that looks painful.  It hits all enemies, so it is more useful against multiple enemies.
Ungarmax: Barret goes all out in a machine gun type attack, unloading an entourage of bullets into an enemy.  It hits more than once.

Level 4
Catastrophe: Uses his gun-arm as a laser cooker, and burns the enemies, causing oodles of damage.  It works very well against both single and multiple enemies.  This is the best of Barret's Limit Breaks.