The dielectronic constant of organic semiconductor materials is directly related to its molecule dipole moment, which can be used to guide the design of high-performance organic photovoltaic materials. Herein, two isomeric small molecule acceptors, ANDT-2F and CNDT-2F, are designed and synthesized by using the electron localization effect of alkoxy in different positions of naphthalene. It is found that the axisymmetric ANDT-2F exhibits a larger dipole moment, which can improve exciton dissociation and charge generation efficiencies due to the strong intramolecular charge transfer effect, resulting in the higher photovoltaic performance of devices. Moreover, PBDB-T:ANDT-2F blend film exhibits larger and more balanced hole and electron mobility as well as nanoscale phase separation due to the favorable miscibility. As a result, the optimized device based on axisymmetric ANDT-2F shows a J(SC) of 21.30 mA cm(-2), an FF of 66.21%, and a power conversion energy of 12.13%, higher than that of centrosymmetric CNDT-2F-based device. This work provides important implications for designing and synthesizing efficient organic photovoltaic materials by tuning their dipole moment.