Decay processes of exciplexes of cyanoanthracenes with alkylbenzene donors were compared to those with alkoxybenzenes. For the three decay processes of exciplexes, the radiative rate constant (kf) of alkoxy derivatives is slightly lower than those of alkylbenzenes at the same average exciplex energy. However, the corresponding deactivation rate constants, intersystem crossing (kisc) and nonradiative decay (knr), are considerably higher. Consequently, the fluorescence quantum yields of the alkoxybenzene exciplexes are one-half to one-fifth of the corresponding alkylbenzenes at comparable emission energies. This trend is solvent-independent. The results can be rationalized in terms of the differing electronic character of the donor radical cation moieties in the alkoxy- vs alkylbenzene exciplexes and differences in their reorganization energies. The impact of these results for the design of exciplexes that emit more efficiently is discussed.