A new benzodithiophene (BDT)-based polymer, poly(4,8-bis(2-ethylhexyloxy)benzo[1,2-b:4,5-b']dithiophene vinylene) (PBDTV), was synthesized by Pd-catalyzed Stille-coupling method. The polymer is soluble in common organic solvents and possesses high thermal stability. PBDTV film shows a broad absorption band covering from 350 nm to 618 nm, strong photoluminescence peaked at 545 nm and high hole mobility of 4.84 x 10(-3) cm(2)/Vs. Photovoltaic properties of PBDTV were studied by fabricating the polymer solar cells based on PBDTV as donor and PC70BM as acceptor. With the weight ratio of PBDTV: PC70BM of 1:4 and the active layer thickness of 65 nm, the power conversion efficiency of the device reached 2.63% with V-oc = 0.71 V, I-sc = 6.46 mA/cm(2), and FF = 0.57 under the illumination of AM1.5, 100 mW/cm(2). (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1822-1829, 2010