Novel donor–π-bridge–acceptor–π-bridge–donor (D–π–A–π–D)-type 1, 4-diketo-3, 6- diphenylpyrrolo [3, 4-c] pyrrole (DPP) derivatives with end-capping diphenylamine groups have been synthesized and shown to exhibit large two-photon absorption cross-sections over a wide range of wavelengths with strong two-photon excitation red fluorescence.