The ground-state EDA complex of (dibenzoylmethanato)boron difluoride (DBMBF(2)) with substituted benzenes (SB) was studied by absorption spectroscopy to determine the equilibrium constant and enthalpy of the molecular association process in acetonitrile and cyclohexane. Excitation of the EDA complexes showed the corresponding exciplex fluorescence due to excitation of DBMBF(2) in the presence of SB. Integration of these data with the previously published kinetics and thermodynamics of the exciplex formation and decay showed that both types of excitations converged on the exciplex energy well and that the former excitation pees through the Franck-Condon state, *(A(-)D(+))(v), which is different in molecular distance and electron and energy distributions. In acetonitrile, the discrepancy of fluorescence intensities from two excitations is taken as proof for electron transfer at the encounter pair on the energy surface to generate radical ions. This also implies that excitation of EDA complexes in acetonitrile forms the corresponding exciplexes directly (without the intermediacy of the encounter pair), which undergo solvolysis to give free ions, A mechanism is proposed to represent the observed photochemistry and photophysics.