A cucurbit[7]uril-based host-guest strategy is employed to enhance the efficiency of photolysis reactions that release caged molecules from photoremovable protecting groups. The photolysis of benzyl acetate follows a heterolytic bond cleavage mechanism, thereby leading to the formation of a contact ion pair as the key reactive intermediate. The Gibbs free energy of the contact ion pair is lowered by 3.06 kcal/mol through the stabilization of cucurbit[7]uril, as revealed by DFT calculations, which results in a 40-fold increase in the quantum yield of the photolysis reaction. This methodology is also applicable to the chloride leaving group and the diphenyl photoremovable protecting group. We anticipate that this research presents a novel strategy to improve reactions involving active cationics, thereby enriching the field of supramolecular catalysis.