A series of novel soluble polythiophene derivatives containing triphenylamine moiety were synthesized by Grignard metathesis (GRIM) method. The structures of the polymers were characterized and their physical properties were investigated. High molecular weight (M-n up to 25,800 g/mol) and thermostable polymers were obtained. The absorption spectra demonstrated that the absorption wavelength of the polymers could be tuned dramatically by introducing thiophene units in the main chain of the polymers. Photoluminescence spectra indicated that there was intramolecular energy transfer from the side chain to the main chain, and the maximum emission was red-shifted gradually with the increase of thiophene units in the main chain. Cyclic voltammetry displayed that the polymers possessed relatively high oxidation potential, which promised good air stability and high open circuit voltage for photovoltaic cells application. Finally, bulk heterojunction photovoltaic devices were fabricated by using the polymers as donors and (6,6)-phenyl C-61-butyric acid methyl ester (PCBM) as acceptor. The maximal open circuit voltage of the photovoltaic cells reached 0.71-0.87 V and the power conversion efficiencies of the devices were measured between 0.014% and 0.45% under white light at 100 mW/cm(2). (c) 2008 Wiley Periodicals, Inc.