We successfully synthesized a series of novel solution processible small molecules (2TAPM, 4TAPM and 2BTAPM) consisting of electron-accepting unit (2-pyran-4-ylidenemalononitrile) (PM) and electron-donating unit (Triphenylamine and different thiophene units). Differential scanning calorimetry (DSC) measurement indicates that these small molecules are amorphous. UV-vis absorption spectra show that the combination of PM with moieties having gradually increased electron-donating ability results in an enhanced intramolecular charge transfer (ICT) transition, leading to an extension of the absorption spectral range and a reduction of the band gap of the molecules. Both cyclic voltammetry measurement and theoretical calculations show that the highest occupied molecular orbital (HOMO) energy levels of the molecules could be fine-tuned by changing the electron-donating ability of the electron-donating moieties. The bulk heterojunction (BHJ) photovoltaic devices with a structure of ITO/PEDOT:PSS/small molecules:PC(71)BM/LiF/Al were fabricated by using the small molecules as donors and (6,6)-phenyl C(71)-butyric acid methyl ester (PC(71)BM) as acceptor. Power conversion efficiencies of 1.76% and 2.47% were achieved for the photovoltaic devices based on 2TAPM:PC(71)BM and 4TAPM:PC(71)BM under simulated air mass 1.5 global irradiation (100 mW/cm(2)), respectively. (C) 2011 Elsevier B.V. All rights reserved.