Poly(3‐hexylthiophene) (P3HT)‐based organic solar cells (OSCs) have attracted much attention due to their advantages of low‐cost production and matured roll‐to‐roll manufacture. However, the efficiency of P3HT‐based OSCs lag much behind the non‐P3HT ones due to their negligible absorption of long wavelengths of light over 650 nm, high‐lying highest occupied molecular orbitals (HOMO), and difficulty of controlling morphology. In this study, the alkyl chains of the nonfullerene acceptors are replaced with alkoxy chains to achieve synergistic enhancement of all three parameters ( short circuit current density (JSC), open circuit voltage (VOC), and fill factor (FF)) and thus significant increase of power conversion efficiency for P3HT‐based OSCs. As a result, the OSCs exhibit a maxima efficiency of 6.6%. The P3HT‐based systems are systematically studied with optical spectroscopy, photoluminescence, cyclic voltametry, space charge limit current, grazing incident wide‐angle X‐ray scattering, transient absorption spectroscopy, transmission electron microscope, and atomic force microscopy to probe the mechanism, which reveal that introducing alkoxy chains simultaneously increases the energy levels of the HOMO and the lowest unoccupied molecular orbitals, enhances the light absorption, improves the rigidity of the backbone and charge transport mobility, and tunes the molecular orientation and film morphology, thus improving the photovoltaic performance. This contribution provides an important guidance in the design of novel nonfullerene acceptors for high‐performance P3HT‐based OSCs.

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