Small molecules, namely, DCAO(3)TBDT and DR3TBDT, with 2-ethylhexoxy substituted BDT as the central building block and octyl cyanoacetate and 3-ethylrhodanine as different terminal units with the same linkage of dioctyltert-thiophene, have been designed and synthesized. The photovoltaic properties of these two molecules as donors and fullerene derivatives as the acceptors in bulk heterojunction solar cells are studied. Among them, DR3TBDT shows excellent photovoltaic performance, and power conversion efficiency as high as 7.38% (certified 7.10%) under AM 1.5G irradiation (100 mW cm(-2)) has been achieved using the simple solution spin-coating fabrication process, which is the highest efficiency reported to date for any small-molecule-based solar cells. The results demonstrate that structure fine turning could cause significant performance difference and with that the performance of solution-processed small-molecule solar cells can indeed be comparable with or even surpass their polymer counterparts.