ABCNews.com has a nice summary description of the electoral college. (Did you know electors vote for the president and vice president individually? Did you know that electors cannot vote for a president and vice president from the same state? Did you know Dick Cheney had to change his voter registration from Texas to Wyoming because of this fact? Well, I didn't.)
For more on "faithless electors," see The US Electoral College Webzine. (Then see the inevitable Metafilter discussion.)