Studies were made on the nature of photoinduced electron transfer (ET) reactions within the electron donor (D) (3,5-dimethylphenol, 35DMP; 2,6-dimethylphenol, 26DMP; 3,5-dimethylanisole, 35DMA; 2,5-dimethylanisole, 25DMA) and acceptor (A) 2-nitrofluorene (2NF) in bath highly polar acetonitrile (ACN) and nonpolar cyclohexane (CH) solvents at 296 K by electronic absorption, steady state, and time-resolved, in the nanosecond time domain, spectroscopic methods. No ground state charge transfer (CT) complex was found for the present D-A pairs. Large fluorescence quenching rates (similar to 10(12) dm(3) mol(-1) s(-1)) were observed in both CH and ACN solvents. Evidence for concurrent occurrence of Forster’s s type singlet-singlet energy transfer process along with ET was found. No static quenching was observed. Radiative energy transfer was found to play an insignificant role within the present D-A systems. Occurrence of highly exothermic outer-sphere type ET reaction within the Marcus inverted region was inferred. In nonpolar CH a contact exciplex of CT nature was observed, whereas in the highly polar ACN environment the anionic radical of the sterically hindered phenol 2,6-DMP was found as final product. At 77 K occurrences of both Forster’s type singlet-singlet and Dexter’s type triplet-triplet energy transfer processes were inferred within the present D-A systems from steady state and time-resolved spectroscopic studies.