Photoremovable protecting groups are of great importance due to their remote control over the liberation of diverse reactive species temporally and spatially, including biologically active compounds and functional groups. Here, an in-depth investigation on the heterolysis-solvolysis reaction mechanisms of a photoremovable protecting group, 3',5'-dimethoxybenzoin (DMB) chloride, has been accomplished. With the aid of transient absorption and time-resolved resonance Raman spectroscopies, the features of the intermediates that emerged from the photolysis process were directly observed. Elaborate optical and theoretical studies on DMB chloride have suggested a long-lived α-keto cation intermediate (0.9 ms) exists as a key intermediate, unlike the radical intermediates that are typically generated in such photocyclization reactions. After undergoing nucleophilic addition and isomerization, the intermediate species eventually leads to the formation of the final product(s).