Pentacene derivatives with both π-radical- and TIPS-substituents (1m and 1p) were synthesized and their photochemical properties and excited-state dynamics were evaluated. The pentacene-radical-linked systems 1m (1p) showed a remarkable improvement in photochemical stability, which was 187 (139) times higher than that of 6,13-bis(triisopropylsilylethynyl)pentacene. Transient absorption spectroscopy showed that this remarkable photostabilization is due to the ultrafast intersystem crossing induced by effective π-conjugation between the radical substituent and pentacene moiety. The relationship between π-topology and the photochemical stability is also discussed based on the excited-state dynamics.