Organic solar cells (OSCs) based on small molecular acceptors (SMAs) have made great development with a power conversion efficiency (PCE) over 16% due to the design of novel materials and advances in device preparation technology. This work fabricates two bulk‐heterojunction photovoltaic devices containing the same wide‐bandgap donor PM6, respectively, matched with popular Y6 and ITIC SMAs. The PM6:Y6‐based device achieves a much higher PCE of 15.21% than the PM6:ITIC‐based device of 9.02%. On the basis of comparisons of macroscopic performances in the quasistatic regime, transient absorption spectroscopy (TAS) is further performed to better understand the microscopic dynamics difference in charge separation processes between the two photovoltaic blends. According to the TAS results, the calculated hole transfer efficiency in PM6:Y6 is 71.4%, far greater than the efficiency of 13.1% in PM6:ITIC, demonstrating favorable charge separation at donor/acceptor interfaces via hole transfer channel in PM6:Y6. The favorable hole transfer in PM6:Y6 is accounted for by its better mutual miscibility between the donor and acceptor, and the formation of long‐lived delocalized intramoiety excimer state in the acceptor. These results highlight the important role of proper molecular design strategy with strong intermolecular coupling and beneficial film morphology on facilitating charge generation in OSCs adopting SMAs. [ABSTRACT FROM AUTHOR]