Three new side-chain conjugated polythiophene derivatives, poly{3-[2-{3-methoxy-4-octyloxy-phenyl)-vinyl]-thiophene} (P3MOPVT), poly{3-[2-(3,5-dimethoxy-4-octyloxy-phenyl)-vinyl]-thiophene} (P3DMOPVT), and poly( 3-[2-(3,4-dioctyloxy-phenyl)-vinyl]-thiophene} (P3DOPVT), were synthesized by Wittig-Hornor reaction and GRIM method and compared with poly{3-[2-(4-octyloxy-phenyl)-vinyl]-thiophene} (P3OPVT) for investigating the effect of the end groups of the conjugated side-chain on the properties of the polymers. Owing to the electron-donating ability of methoxy groups, the visible absorption peaks of P3MOPVT and P3DMOPVT solutions and films become stronger and red-shifted compared with P3OPVT. The electrochemical bandgaps of the four polymers are 2.15 eV for P3OPVT, 1.99 eV for P3MOPVT, 1.85 eV for P3DMOPVT, and 2.36 eV for P3DOPVT, respectively, which indicate that the electron-donating ability of the methoxy end group on the conjugated side chain of P3MOPVT and P3DMOPVT and the large steric hindrance of the two octyloxy end groups on the conjugated side chain of P3DOPVT have obvious influence on the electrochemical properties of the side-chain conjugated polythiophenes. Polymer solar cells were fabricated with a structure of ITO/PEDOT:PSS/Polymer:PCBM/LiF/Al. The best device, based on P3DMOPVT, shows a power conversion efficiency of 1.63% under the illumination of AM1.5, 80 mW/cm(2). (c) 2006 Wiley Periodicals, Inc.