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Organic solar cells (OSCs) processed with non‐halogenated solvents usually suffer from excessive self‐aggregation of small molecule acceptors (SMAs), severe phase separation and higher energy loss (Eloss), leading to reduced open‐circuit voltage (Voc) and power conversion efficiency (PCE). Regulating the intermolecular interaction to disperse the aggregation and further improve the molecular packing order of SMAs would be an effective strategy to solve this problem. Here, we designed and synthesized two SMAs L8‐PhF and L8‐PhMe by introducing different substituents (fluorine for L8‐PhF and methyl for L8‐PhMe) on the phenyl end group of the inner side chains of L8‐Ph, and investigated the effect of the substituents on the intermolecular interaction of SMAs, Eloss and performance of OSCs processed with non‐halogenated solvents. Through single crystal analysis and theoretical calculations, it is found that compared with L8‐PhF, which possesses strong and abundant intermolecular interactions but downgraded molecular packing order, L8‐PhMe with the methyl substituent possesses more effective non‐covalent interactions, which improves the tightness and order of molecular packing. When blending the SMAs with polymer donor PM6, the differences in intermolecular interactions of the SMAs influenced the film formation process and phase separation of the blend films. The L8‐PhMe based blend film exhibits shorten film formation and more homogeneous phase separation than those of the L8‐PhF and L8‐Ph based ones. Especially, the OSCs based on L8‐PhMe show reduced non‐radiative energy loss and enhanced Voc than the devices based on the other two SMAs. Consequently, the L8‐PhMe based device processed with o‐xylene (o‐XY) and using 2PACz as the hole transport layer (HTL) shows an outstanding PCE of 19.27 %. This study highlights that the Eloss of OSCs processed with non‐halogenated solvents could be decreased through regulating the intermolecular interactions of SMAs by inner side chain modification, and also emphasize the importance of effectivity rather than intensity of non‐covalent interactions introduced in SMAs on the molecular packing, morphology and PCE of OSCs. [ABSTRACT FROM AUTHOR]