Organic small molecules (TPA-BT3T, TPA-PT3T, and TPA-DFBT3T) using triphenylamine as a donor unit, terthiophene as a bridge, and benzo-2,1,3-thiadiazole (BT), [1,2,5]thiadiazolo[3,4-c]pyridine (PT) or 5,6-difluorobenzo[c][1,2,5]thiadiazole (DFBT) as an acceptor unit were designed and synthesized through Suzuki coupling reactions. These molecules exhibited good thermal stability with decomposition temperatures over 380 oC and broad absorption from 300 to 700 nm. Photovoltaic devices were fabricated with these small molecules as donors and PC71BM as an acceptor. The TPA-BT3T based devices exhibited a power conversion efficiency of 2.89%, higher than those of the TPA-PT3T- and TPA-DFBT3T-based devices (1.34% and 1.54% respectively). The effects of electron-withdrawing units on absorption, energy level, charge transport, morphology, and photovoltaic properties also were investigated.