I think I remember that the last major changes were in 1492, when pawns were given the ability to move forward two squares on the first move instead of just one, and en pessant was added to deal with that. That's also around the time that castling was added and the queen became so powerful, as it had been a much weaker piece previously. I don't remember where I heard that specific year, but I remember that it was the same year that Columbus reached the Americas, which is why the year stood out to me.
A more minor rules change that I know about is white being given the first move. Apparently, in the 19th century, black sometimes moved first. Because the board's symmetric, that doesn't actually affect game play, so I consider that one minor.
Also, I know the way draws were counted in tournaments has changed along the way, though counting it as half a win has been the most common practice for probably around a century now.
--Fromper