In this paper, we investigate the effects of solvation on the solar energy storage properties of bicyclooctadiene/tetracyclooctane (BOD/TCO) photoswitches. The solvent effects on the thermochemical and optical properties are studied in cyclohexane, toluene, dichloromethane, ethanol, acetonitrile, and a vacuum using density functional theory and coupled cluster theory. Our results show that the energy storage capacity of the BOD/TCO system increases as the solvent polarity increases, and the change is more significant with an unsubstituted system. The energy storage capacity of the substituted system is not dependent on the polarity of the solvent. As the solvent polarity increases, the absorption peaks shift away from each other and the absorption intensities increase. Overall, the solvents improve the performance of the optical properties and the energy storage capacities of the BOD/TCO molecular solar thermal systems.