Two soluble acceptor-donor-acceptor (A-D-A) type organic small molecules, 2,2'-(5,5'-(1E,1'E)-2,2'-(benzo[c][1,2,5]thiadiazole-4,7-diyl)bis(ethene-2,1-diyl)bis(3,4-dihexylthiophene-5,2-diyl))bis(methan-1-yl-1-ylidene)dimalononitrile (BvT-DCN) and 2,2'-(3,3'-(1E,1'E)-2,2'-(5,5'-(1E,1'E)-2,2'-(benzo[c][1,2,5]thiadiazole-4,7-diyl)bis(ethene-2,1-diyl)bis(3,4-dihexylthiophene-5,2-diyl))bis(ethene-2,1-diyl)bis(5,5-dimethylcyclohex-2-ene-3-yl-1-ylidene))dimalononitrile (BT-C6), were synthesized by Knoevenagel condensation reaction based on benzothiadiazole, thiophene, and different terminal electron-withdrawing groups. The acceptor group benzothiadiazole and donor group thiophene inside the molecules are connected by all-trans double bonds, which ensures the benzothiadiazole and thiopene groups are in the same plane and makes the molecules have a relative narrow band gap and absorb sunlight in the long wavelength. The terminal electron-withdrawing groups, malononitrile and 2-(5,5-dimethylcyclohex-2-en-1-ylidene)malononitrile (DCM), are symmetrically introduced into the molecules, respectively, to tune the energy level and extend the absorption of the molecules. The UV-Vis absorption spectrum and cyclic voltammetry measurements indicated that BT-C6 has a lower energy band gap (1.60 eV) than BvT-DCN (1.71 eV), which arises from the stronger electron-withdrawing ability of DCM group in BT-C6 than that of malononitrile group in BvT-DCN. And BvT-DCN and BT-C6 have nearly the same highest occupied molecular orbital energy level, -5.74 eV for BvT-DCN and -5.72 eV for BT-C6 due to the same electron-donor group of the two compounds. Bulk heterojunction photovoltaic devices were fabricated using BvT-DCN or BT-C6 as donor and (6,6)-phenyl C-61-butyric acid methyl ester as acceptor. The device based on BT-C6 has a higher (8 times) short circuit current and power conversion efficiency than the device based on BvT-DCN, resulting from the wider solar light absorption of BT-C6 and smaller phase separation dimension of the active layer based on BT-C6.