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). 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 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. It is found that compared with L8-PhF, which possesses strong intermolecular interactions but downgraded molecular packing order, L8-PhMe exhibits more effective non-covalent interactions, which improves the tightness and order of molecular packing. When blending the SMAs with PM6, the OSCs based on L8-PhMe shows 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 and using 2PACz as the hole transport layer 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.