New symmetrical low band-gap small molecule materials, SQ-bis[HP-HT2-TPA] and SQ-bis[HP-HT2-BT] incorporating as novel derivative of squaraine-pyrrole framework and pi-extended thiophene with triphenyamine (TPA) and benzothiophene (BT) end group, have been synthesized and characterized. The effects of TPA moiety were investigated. Compared to SQ-bis[HP-HT2-BT], SQ-bis[HP-HT2-TPA] exhibited three times improved transporting property of hole carrier and four times enhanced absorptivity by more efficient intermolecular pi-pi it interaction for high-efficiency bulk heterojunction (BHJ) device, suggesting that TPA contributes to a better hole mobility. The bulk-heterojunction photovoltaic devices fabricated with SQ-bis[HP-HT2-TPA]/C(71)-PCBM BHJ] film had an average power-conversion efficiency of 1.83%(+/- 0.12) under 100 mW/cm(2), with a short-circuit cur +/- rent (J(sc)) of 9.32 mA/cm(2), fill factor (FF) of 0.30, and open-circuit voltage (V(oc)) of 0.65 V. which has similar to 42% higher efficiency compared to SQ-bis[HP-HT2-BTI/C(71)-PCBM BHJ films. (C) 2011 Elsevier B.V. All rights reserved.