Three two-dimensional (2-D) conjugated polythiophenes with bi(thienylenevinylene) side chains (biTV-PTs), P1, P2, and P3, were designed and synthesized for application in polymer solar cells. The absorption spectral, electrochemical, and photovoltaic properties of the biTV-PTs were investigated and compared with those of poly(3-hexylthiophene) (P3HT). The biTV-PTs show a broad absorption band from 350 to 650 nm; especially, the absorption spectrum of P3 displays a broad plateau and much stronger absorbance than that of P3HT in the wavelength range from 350 to 480 rim. Cyclic voltammograms reveal that the onset oxidation and reduction potentials of the biTV-PTs positively shifted by ca. 0.2 V in comparison with those of P3HT, indicating that the HOMO energy level of the biTV-PTs is ca. 0.2 eV lower than that of P3HT. Polymer solar cells (PSCs) were fabricated based on the blend of the polymers and 1-(3-methoxycarbonyl)propyl-1 -phenyl-[6,6]-C-61 (PCBM) with a weight ratio of 1:1. The open circuit voltage of the PSCs based on the biTV-PTs is ca. 0.1 V higher than that of P3HT, which is benefited from the lower HOMO levels of the biTV-PTs. The maximum power conversion efficiency (PCE) of the PSCs based on P3 reached 3.18% under AM 1.5, 100 mW/cm(2), which is 38% increased in comparison with that (2.41%) of the devices based on P3HT under the same experimental conditions. The results indicate that the 2-D conjugated biTV-PTs are promising polymer photovoltaic materials.