Free ion yields from geminate ion pairs formed after photoinduced electron transfer are measured by the transient photocurrent method in three moderately polar solvents. Photoexcited 9,10-dicyanoanthracene (DCA) is used as the electron acceptor and alkyl-substituted benzenes as donors. It was found that, generally, there is no significant change in free ion yield as the temperature is increased. On the basis of a theoretical model developed under Collins-Kimball boundary conditions, several factors are analyzed, including dielectric constants and viscosities of solvents, initial separation distance distribution of geminate ion pairs, and temperature-induced changes in recombination rates. By comparing escape probabilities of geminate ion pairs calculated at different initial formation and recombination/separation distances with measured free ion yields, we show that free ions are mainly produced from the solvent-separated ion pairs that are initially formed after electron transfer quenching of photoexcited DCA. Calculations also imply that recombination via electron tunneling at separation distances of about 7.5 Angstrom can be considered as the main decay process for solvent-separated ion pairs. There is a direct competition between tunneling recombination and further separation of ion pairs at each distance. Experimental photocurrent rise times indicate that the change in temperature has very limited influence on the recombination rates. On the other hand, an increase in temperature will decrease the viscosities of the solvents and thus increase the mobility of cations and anions significantly, which will, in turn, increase the escape rate and free ion yields. Quantitative analysis indicates that the observed weak dependence of free ion yields on temperature can be attributed to an unfavorable contribution from the decreased dielectric constant at higher temperature.