Picosecond laser photolysis reveals the formation of an exciplex between the lowest excited singlet state [DBA*(S-1)] of 9,10-dibromoanthracene (DBA) and ground-state amine in acetonitrile (CH3CN) and ethanol (EtOH) containing N,N-dimethylaniline (DMA) [and n-heptane (HP) containing DMA or triethylamine (TEA)]. Only in CH3CN-DMA, however, can decomposition of the DBA-DMA exciplex into the DBA radical anion (DBA(.-)) and the DMA radical cation be seen, indicating very small generation of DBA(.-) from the DBA-amine exciplex formed in EtOH-DMA and HP-amine (DMA or TEA). Interestingly, no DBA-TEA exciplex is formed in CH3CN and EtOH containing TEA but nanosecond laser photolysis reveals the existence of DBA(.-) in the former solvent. Furthermore, the rate of DBA --> 9-bromoanthracene debromination upon steady-state photolysis in CH3CN-TEA is 1 order of magnitude smaller than that in CH3CN-DMA but 2 or 3 orders of magnitude greater than those in EtOH and HP containing amine. This suggests that diffusion-controlled quenching of DBA*(S-1) by TEA in CH3CN and EtOH gives rise to the formation of a nonemissive short-lived encounter complex or ion pair. It thus be concluded that generation of DBA(.-) from the DBA-amine exciplex or the encounter complex (or the ion pair) is affected by the dielectric constant of a pure solvent.