A solution-processable and star-shaped molecule 4-((E)-2-(benzo[1,2,5]thiadiazol-4-yl)vinyl)-N,N-bis(4-((E)-2-(benzo[1,2,5]thiadiazol-7-yl)vinyl)phenyl)benzenamine (TPA-BT) has been designed and synthesized by palladium-catalyzed Heck reaction for the application in organic solar cells (OSCs). The molecule possesses a D–A structure with a triphenylamine core (donor unit) linked with three benzo[1,2,5]thiadiazole (acceptor unit) arms through double bonds. TPA-BT film shows a strong absorption peak in the visible wavelength range from 400 to 560 nm, which could be ascribed to the charge transfer band of the D–A structure of the molecule. The bulk-heterojunction OSCs with the device structure of ITO/PEDOT:PSS/TPA-BT:PCBM/Ca/Al (or Ba/Al) were fabricated by spin-coating the blend solution of TPA-BT and PCBM (1:3, w/w), in which TPA-BT was used as donor and PCBM as acceptor materials. The devices show a high open circuit voltage of ca. 0.9 V and a power conversion efficiency of 0.61%, under the illumination of AM 1.5, 100 mW/cm 2. The results indicate that TPA-BT is a promising solution-processable organic photovoltaic material.