Two organic small molecules based on diketopyrrolopyrrole (DPP) units having a D-A-D-π-D-A-D structure denoted as and were synthesized. Their optical and electrochemical properties relevant to organic solar cells were investigated. The wider optical absorption coverage from 450-800 nm, the highest occupied molecular orbital (HOMO) (-5.23 eV and -5.34 eV for and , respectively) and the lowest unoccupied molecular orbital (LUMO) (-3.47 and -3.45 eV for and , respectively) make these small molecules suitable as donors for bulk heterojunction organic solar cells. The bulk heterojunction (BHJ) organic solar cells based on an active layer consists of a blend of these small molecules as donors and PC71BM as an acceptor with an optimized weight ratio of 1 : 2 cast from chloroform (CF) showed overall power conversion efficiencies (PCEs) of 1.98% (with Jsc = 5.38 mA cm(-2), Voc = 0.84 V and FF = 0.42) and 1.85% (with Jsc = 4.56 mA cm(-2), Voc = 0.96 V and FF = 0.42) for and respectively. The relatively high Voc value based on the based device has been attributed to the deeper HOMO of compared to . The optimized : PC71BM (1 : 2) and : PC71BM (1 : 2) active layers were subjected to two step annealing (TSA), i.e. thermal annealing and subsequent solvent vapor annealing and the corresponding BHJ organic solar cells showed a PCE of 5.28% (Jsc = 11.53 mA cm(-2), Voc = 0.79 V and FF = 0.58) and 5.52% (Jsc = 10.84 mA cm(-2), Voc = 0.91 V and FF = 0.56), respectively. The enhancement in PCE is mainly due to the improvement in Jsc and FF, related to light absorption in an active layer, a better nanoscale morphology, and an increase in the crystalline nature of the active layer and balanced charge transport, induced by the TSA treatment.