The use of nonlinear optical processes expands the flexibility of excimer systems in the study of a wide range of atomic and molecular phenomena and materials. These mechanisms have already allowed for the selective excitation of states in the 10 to 20 eV range involving bound state excitation, ionization, and molecular dissociation. Specific examples involving the electronic excitation of Hz, Kr, and Xe, the production of Xe+ for the analysis of the molecular properties of X@*, and nonlinear photodissociation of N2O and OCS are discussed.