The biggest thing for me is overcoming the mental challenge that last 20 miles. You can train, do 60-70 milers with ease, have confidence, good nutrition, good sleep, take a few days off before, take breaks during the 100 miler, take your time, keep hydrated.... all of that. But for me, at around 80 miles, and especially 85 miles on, man, that is when my mind starts working against me. My butt is sore, muscles all used up, tired of pedaling, tire of riding and just want to quit. My mind starts saying, "you can't make it" and "what's the point, just go ahead and quit now". It's all in my head at that point and the struggle becomes, defeating negative thoughts AND STILL staying focused on what I'm doing. It's easy to get sloppy and quit paying attention to what's going on around you.
At the end, it's all worth it. Lift you bike over your head and let out a yell! Then go sit in a hot tub with a beer.