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 × 10−3 cm2/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 Voc = 0.71 V, Isc = 6.46 mA/cm2, and FF = 0.57 under the illumination of AM1.5, 100 mW/cm2. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1822–1829, 2010