In model studies involving the mechanisms of DNA photolyases, two reverse solvent effects on the quantum yield of photosensitized splitting of a cyclobutane pyrimidine dimer (CPD) by a covalently linked chromophore have been reported. One is an increase in the splitting efficiency in lower polarity solvents for model compounds with a short linker between the dimer and the chromophore. Another is more efficient splitting in higher polarity solvents for model compounds with a flexible and long linker. To unravel mechanisms of two opposite solvent effects, five covalently linked indole-dimer compounds with different-length linkers were prepared. Two solvent effects as described above were observed through measuring quantum yields of dimer splitting of these model compounds in four solvents. According to Marcus theory, back electron transfer in the splitting reaction was analyzed quantitatively in light of relative data of a model compound in four solvents. It was demonstrated that the dependence of the quantum yield on solvent polarity for the flexible long-linker system would derive from the change in the distance between a dimer unit (acceptor) and an indole moiety (electron donor) in different solvents. With increasing solvent polarity, a U-shaped conformation of the model compound would become a preferred conformation because of the hydrophobic interaction between indole and dimer moiety, and their distances would become closer. On the basis of Marcus theory, calculated results reveal that the rate of back electron transfer would be slowed down with increasing solvent polarity and the distance reduced, giving a more efficient splitting. Meanwhile, some, new insights into mechanisms of DNA photoreactivation mediated by photolyases were gained.