I can't recall who Louis's first wife was, but whoever she was, he divorced her to marry Anne of Brittany, who was the widow of his predecessor Charles. There were rumors at the time that Louis and Anne had been lovers during Anne's marriage to Charles, but more likely Louis married Anne to retain possession of her duchy of Brittany, which otherwise would pass out of French control. Anne and Louis had two daughters, Claude and Renee, but no sons. Claude married Francois d'Angouleme, Louis's cousin and heir. I don't remember who Renee married, but at one point she was considered as a possible bride for Henry VIII. I think she was Wolsey's preferred candidate, but of course nothing came of it since Henry had already decided that Anne Boleyn would be wife no. 2.
Supposedly Louis was absolutely besotted with Henry VIII's young sister Mary, his third wife. She, however, wasn't too happy with the situation and made it her mission to exhaust Louis with an endless round of dancing and partying. He died within months of marrying Mary, and she eloped with a handsome commoner, Charles Brandon, with whom she had been in love previously. She continued to be known as the French Queen even after her marriage to Charles Brandon, and was the second lady at Henry VIII's court after Catherine of Aragon, the queen.
The only other thing I can remember about Louis is that he didn't get along terribly well with Ferdinand of Aragon, which stands to reason given the traditional enmity between France and Aragon. They did, however, come to a temporary understanding in 1505 or so, when Ferdinand was quarreling with his son in law Philip the Handsome over the throne of Castile. Louis and Philip had been allies, but then when Philip cut a deal with Henry VII of England, Louis decided that Philip was getting altogether too big for his britches and formed an anti-Philip alliance with Ferdinand to keep the balance of power a little more, um, balanced. Anyway, as part of the alliance Louis gave Ferdinand his kinswoman Germaine de Foix to be Ferdinand's second wife. She was 18; Ferdinand was pushing 50 at the time. Seems to have been a trend back in those days.