A star-shaped oligothiophene based on triphenylamine as a core and 2-ethylhexyl cyanoacetate as end groups (S(TPA-3T-CA)) was synthesized. S(TPA-3T-CA) exhibited strong absorption and high hole mobility. Solution-processed solar cells based on S(TPA-3T-CA):PC(71)BM showed a power conversion efficiency of 3.60% and a fill factor of 0.56.