The bench press is probably the most well known one. People say doing them with dumbells instead of a barbell cant be better. There the flat, incline and decline Simo mentioned. You could also try flies, which don't use the triceps like the benchpress does.
bench press is king exercice for the upper body. Add Butterflies to add a different kind of exercice (like Taliq said, no triceps and over all a different approach) and you'll be fine.