A novel conjugated polymer, poly(thienylene-vinylene-thienylene) with cyano substituent (CN-PTVT) was synthesized via Stille coupling for the application in air stable field-effect transistor and polymer solar cell. The polymer was characterized by H-1 NMR, elemental analysis, UV-vis absorption and photoluminescence spectroscopy, TGA, cyclic voltammetry and XRD analysis. CN-PTVT exhibits a good thermal stability with 5% weight loss at 306 degrees C. The FET hole mobility of the polymer reached 5.9 x 10(-3) cm(2) V-1 s(-1) with I-on/I-off ratio of 4.9 x 10(4), which is one of the highest performance among the air-stable amorphous polymers. The polymer solar cell based on CN-PTVT as donor and PCBM as acceptor shows a relatively high open-circuit voltage of 0.82 V and a power conversion efficiency of 0.3% under the illumination of AM1.5, 100 mW/cm(2). (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4028-4036, 2009