A series of xanthene dyes bearing a tert-butyl peroxybenzoate moiety was synthesized. The fluorescence and phosphorescence spectra were measured to determine the photoproperties of xanthene dye peresters. The transient phenomena were also examined by nanosecond laser flash photolysis in organic solvents at room temperature. Furthermore, the photodecomposition behavior of these compounds was followed by UV-VIS absorption and the final decomposition products were distinguished by comparing IR spectra before and after the irradiation with an Ar⁺ laser at 514.5 nm. To prove their application to information recording materials, the sensitivities for the visible light initiating system are also reported.