Additives play a crucial role in enhancing the photovoltaic performance of polymer solar cells (PSCs). However, the typical additives used to optimize blend morphology of PSCs are still high boiling-point solvents, while their trace residues may reduce device stability. Herein, an effective strategy of "solidification of solvent additive (SSA)" has been developed to convert additive from liquid to solid, by introducing a covalent bond into low-cost solvent diphenyl sulfide (DPS) to synthesize solid dibenzothiophene (DBT) in one-step, which achieves optimized morphology thus promoting efficiency and device stability. Owing to the fine planarity and volatilization of DBT, the DBT-processed films achieve ordered molecular crystallinity and suitable phase separation compared to the additive-free or DPS-treated ones. Importantly, the DBT-processed device also possesses improved light absorption, enhanced charge transport, and thus a champion efficiency of 11.9% is achieved in the PM6:Y6-based PSCs with an excellent additive component tolerance, reproducibility, and stability. Additionally, the DBT-processed PM6:L8-BO-based PSCs are further fabricated to study the universality of SSA strategy, offering an impressive efficiency approaching 19% as one of the highest values in binary PSCs. In conclusion, this article developed a promising strategy named SSA to boost efficiency and improve stability of PSCs.