We report herein the solvent and temperature effects on the emission of the intermolecular exciplexes 1-cyanonaphthalene/triethylamine and 1-methylnaphthalene/triethylamine and the intramolecular exciplexes formed by the bichromophoric compounds diethyl-(3-naphthalen-1-yl-propyl)-amine (I), diethyl-(2-naphthalen-1-yl-ethyl)-amine (II), 3-[ethyl-(2-naphthalen-1-yl-ethyl)-amino]-propionitrile (III) and 3-[(2-cyano-ethyl)-(2-naphthalen-1-yl-ethyl)-amino]-propionitrile (IV). The results are interpreted within the formalism of the semiclassical Marcus theory for radiative back electron transfer (BET) reactions. We show that, following a few simple assumptions, reliable values of the Gibbs free energy changes (ΔG^ε_−et) and the solvent reorganization energies (λ^ε_s) associated to the BET reactions (and their corresponding enthalpic and entropic contributions) can be estimated directly from the emission of the CT states. We also show that for the 1-cyanonaphthalene/triethylamine exciplex, which exhibits emission in the vapour phase, the experimental calculation of the absolute energy of solvation of the CT state (ΔG^ε_s) is also possible. The calculated ΔG^ε_−et correlate quite satisfactorily with the corresponding values obtained from independent electrochemical and kinetics experiments. The temperature effects on ΔG^ε_−et, λ^ε_s and ΔG^ε_s are discussed qualitatively using different solvation models. The limitations of the present approach for the estimation of ΔG^ε_−et and λ^ε_s and its possible application to more complex A/D systems are also examined.