I disagree about the Miami-FSU rivalry, which is definitely one of the great rivalries of sport. It's simply not true that Miami has never been FSU's biggest game. The 1991, 1992, 2000, 2002, 2004, and 2005 Wide Right/Left/botched field goal games speak to this, and the first four of those games had national title implications, FSU being denied titles in '91, '92 because of losing that. I actually think this rivalries has produced the (second) most consistently entertaining game, with so many outcomes being decided by a field goal or less.
First most entertaining? UGA v. Ga Tech. I don't know what the Florida-Georgia pick is about, because Georgia's biggest rival is Georgia Tech, and this is a rivalry that has produced tons of heart-pounding games and is as huge in North Georgia as Auburn-Alabama is in that state, and more intense than UCLA-USC. This is probably the most undervalued rivalry.
Florida-FSU deserves mention, USC-Notre Dame used to be more important, but it still belongs as well. The glaring omission here is Cal-Stanford. The hatred between the two schools is monumental, and of course, this rivalry produced the single greatest college football game of all time in 1982.
All the other games on ESPN's list are valid, except for the Leighigh-Lafayette and Harvard-Yale games. I'm sorry, but if the students don't care about the game, it's not a rivalry. Empty seats in a rivalry game? Not exactly intense.