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A small molecule TBTT-1 with 5-(2-ethylhexyl)-1,3-bis(2-(2-ethylhexyl)thieno[3,4-b]thiophen-6-yl)-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione (TBTT) as the central moiety was designed and synthesized for solution-processed bulk-heterojunction solar cells. TBTT-1 exhibits a broad absorption with a low optical band gap of approximately 1.53 eV in the thin film. An optimized power conversion efficiency (PCE) of 7.47% with a high short-circuit current of 14.95 mA cm^–2 was achieved with diphenyl ether (DPE) as additive, which is the highest PCE for TPD-based small-molecule solar cells. According to the detailed morphology investigations, we found that DPE processing helped to enhance π–π stacking and reduce the scales of phase separation, which led to improved exciton splitting and charge transport in BHJ thin film, and thus enhanced device performance.