Two novel copolymers containing PPV and triphenylamine moieties connected at 1,7 bay positions of perylene bisimide were successfully synthesized by means of the Wittig reaction. Both of them were characterized by FT-IR, H-1 NMR, UV-vis, and FL spectra as well as GPC, TGA, and DSC measurements. The introduction of PPV and TPA moieties into the bay positions of perylene bisimide enhanced the solubility of polymers and quenched the fluorescence of perylene bisimide obviously. The photovoltaic devices ITO/PEDOT:PSS/copolymers/Ca/Al were fabricated, and their I-V characteristics indicated that the copolymerization in PERY-PPV and PERY-PPV-TPA improved the device performance for some extent.