Due to the high exciton binding energy and relatively low charge carrier mobilities of organic photovoltaic materials, it is crucial to optimize the active layer morphology of organic solar cells (OSCs) to well juggle exciton dissociation and charge carrier transport, and inhibit charge carrier recombination for high power conversion efficiencies (PCEs). Herein, we efficiently improve the crystallinity and miscibility of fused ring electron acceptors (FREAs) via lengthening the side chains and developing four FREAs, BTP-nC8, BTP-C8, BTP-C12 and BTP-C20. The dual functions of lengthening the side chains of FREAs make PM6:FREA blend films present the tendency of first improving then deteriorating in crystallinity, phase separation, domain purity and thus charge carrier dynamics, which leads the JSC and FF of PM6:FREA-based OSCs to show the same trend along with the side-chain length of FREAs. More importantly, enhancing the miscibility between PM6 and FREA facilitates the spatial registry to reduce the formation and recombination rate of triplet excitons in the PM6:FREA blend films, thus inhibiting the non-radiative recombination for decreased Delta Enr, and then increasing VOC in OSCs. Among them, PM6:BTP-C8 based OSCs well balance the multiple impacts of lengthening the side chains to achieve the highest PCE of 17.77%. This work demonstrates that it is important to finely control the crystallinity and miscibility of organic photovoltaic materials to achieve high PCEs in OSCs. The miscibility and crystallinity of fused ring electron acceptors is regulated to study the effects on the morphology and energy loss of organic solar cells (OSCs). BTP-C8 based OSCs juggle multiple impacts to gain the best efficiency.