Power conversion efficiency (PCE) of organic solar cells (OSCs) processed by nonhalogenated solvents is unsatisfactory due to the unfavorable morphology. Herein, two new small molecule acceptors(SMAs) Y6-Ph and L8-Ph are synthesized by introducing a phenyl end group in the inner side chains of the SMAs of Y6 and L8-BO, respectively, for overcoming the excessive aggregation of SMAs in the long-time film forming processed by nonhalogenated solvents. First, the effect of the film forming time on the aggregation property and photovoltaic performance of Y6, L8-BO, Y6-Ph, and L8-Ph is studied by using the commonly used solvents: chloroform (CF) (rapid film forming process) and chlorobenzene (CB) (slow film forming process). It isfound that Y6- and L8-BO-based OSCs exhibit a dramatic drop in PCEfrom CF- to CB-processed devices owing to the large phase separation, while the Y6-Ph and L8-Ph based OSCs show obviously increased PCEs Furthermore, L8-Ph-based OSCs processed by nonhalogenated solvent o-xylene (o-XY) achieved a high PCE of 18.40% with an FF of 80.11%. The results indicate that introducing a phenyl end group in the inner side chains is an effective strategy to modulate the morphology and improve the photovoltaic performance of the OSCs processed by nonhalogenated solvents.