To evaluate the effect of side chain characteristics on the photovoltaic performance of small molecules containing both benzodithiophene (BDT) and thienopyrroledione (TPD), we designed and synthesized two such molecules, one containing a branched 2-ethylhexyl (2EH) side chain on the BDT unit (BDTEH-TTPD) and the other containing a linear n-octyl (C8) side chain on the BDT unit (BDTO-TTP). The optical and electrochemical properties and crystalline structures of these molecules were examined. Compared to BDTO-TTPD, BDTEH-TTPD, showed stronger light absorption, longer-range ordering and shorter π-π stacking distances between backbones. As a result, the power conversion efficiency of a bulk heterojunction solar cell based on BDTEH-TTPD (2.40%) was substantially higher than that of the BDTO-TTPD device (1.12%).