Molecular innovation is highly desirable to achieve efficient all-small-molecule organic solar cells (SM-OSCs). Herein, three small-molecule donors (SMDs) with alkylated thiazole side groups (namely BO-1, HD-1, and OD-1), which differ only in the alkyl side chain are reported. Although these SMDs possess similar absorption profiles and molecular energy levels, their crystallinity and miscibility with BTP-eC9 slightly decrease along with the elongation of the alkyl side chain. After blending with BTP-eC9, different miscibility leads to different degrees of phase separation. Among these SM-OSCs, the HD-1-based device shows a decent bulk-heterojunction (BHJ) morphology with proper phase separation and more dynamic carrier behavior. Thus, compared to the BO-1 and OD-1-based devices, the HD-1-based device achieves a higher short-circuit current of 26.04 mA cm(-2) and a fill factor of 78.46%, leading to an outstanding PCE of 17.19%, which is one of the highest values among SM-OSCs. This work provides a rational design strategy of SMDs for highly efficient SM-OSCs.