Two new triindole-cored star-shaped molecules SM-1 and SM-2 have been designed and synthesized, and their optical, electrochemical, thermal, transport and photovoltaic properties have been investigated in detail. SM-1 and SM-2 exhibited good thermal stability, intensive absorption in a broad region, and relatively high hole mobility. Photovoltaic performances of these two molecules were investigated by fabricating bulk heterojunction solar cell devices with a blend film of SM-1:PC₇₁BM or SM-2:PC₇₁BM as the active layer. Organic solar cells (OSCs) based on SM-1:PC₇₁BM and SM-2:PC₇₁BM gave power conversion efficiencies (PCEs) of 2.05% and 2.29%, respectively. A PCE of 2.29% is the best result for all the reported triindole-based photovoltaic materials, indicating that triindole-based small molecules could become promising donor materials for solution-processed OSCs.