To clearly show how important the impact of side chains on organic solar cells (OSCs) is, we designed three acceptors IDIC-CxPh (x = 4, 5, or 6) via subtle side-chain regulation. Despite this small change, significant distinctions were detected. IDIC-C4Ph devices achieve an optimal efficiency of 13.94% under thermal annealing, but thermal-assistant solvent-vapor annealing hugely suppresses the efficiencies to 10%. However, the C6Ph side chain endows extremely disordered stacking orientations, generating moderate efficiencies of ~12.50%. Excitingly, the IDIC-C5Ph affords an unexpected two-channel π-π charge transport (TCCT) property, boosting the fill factor (FF) by up to 80.02% and efficiency to 14.56%, ranking the best among five-ring fused-ladder-type acceptors. Impressively, the special TCCT behavior of IDIC-C5Ph enables 470 nm thick-film OSC with a high FF of up to 70.12% and efficiency of 13.01%, demonstrating the great promise in fabricating large-scale OSCs. Display omitted •OSCs are a promising technology to transform the solar energy to electricity•This article reports an efficient TCCT photovoltaic material through subtle side-chain modification•The TCCT property enables 13% efficiency with FF reaching 70% in 470 nm thick-film photovoltaics