Two poly(thiazole vinylene) derivatives, poly(4-hexylthiazole vinylene) (P4HTzV) and poly(4-nonylthiazole vinylene) (P4NTzV), were synthesized by Pd-catalyzed Stille coupling method. The polymers are soluble in common organic solvents such as o-dichlorobenzene and chloroform, and possess good thermal stability. P4HTzV and P4NTzV films exhibit broad absorption bands at 400720 nm with an optical bandgap of 1.77 eV and 1.74 eV, respectively. The HOMO (the highest occupied molecular orbital) energy levels of P4HTzV and P4NTzV are -5.11 and -5.12 eV, respectively, measured by cyclic voltammetry. Preliminary results of the polymer solar cells based on P4HTzV : PC61BM ([6,6]-phenyl-C-61-butyric acid methyl ester) (1 : 1, w/w) show a power conversion efficiency of 0.21% with an open-circuit voltage of 0.55 V and a short circuit current density of 1.11 mA cm(-2), under the illumination of AM1.5G, 100 mW cm(-2). (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012