The reversible proton dissociation and geminate recombination of photoacids is studied as a function oftemperature in alcohols. For this purpose we used a strong photoacid 5,8-dicyano-2-naphthol (DCN2) (p∼ −4.5 in water) that is capable to transfer a proton to alcohols. The experimental data are analyzed by theDebye−Smoluchowski equation solved numerically with boundary conditions to account for the reversibilityof the reaction. We propose a qualitative model to describe the unusual temperature dependence of the proton-transfer rate constant in alcohols in the liquid phase.