Gambits are 'programmable' actions which characters in your party follow to a T. For instance, if you order a part a-member to attack the target of the party leader, he or she will only attack once the leader has targeted the enemy.
When can I use Gambits ff12?
Gambits are available once Penelo joins the party, though the player has to wait until Balthier and Fran join to be able to customize gambits.
How do you do Gambits?
The basic Gambit loop is pretty simple: kill dudes, get motes, bank motes, repeat until Primeval. Banking motes is a pretty key part of that process, and it's the one you'll see people mess up the most.