Traditional organic photovoltaic materials exhibit low dielectric constants (ε_r) of 3 to 4, restricting the further enhancement of power conversion efficiencies (PCEs) of organic solar cells (OSCs). Herein we design and synthesize a fused-ring electron acceptor named Y6-4O through introducing an asymmetric highly polarizable oligo(ethylene glycol) side chain onto the pyrrole unit of Y6. Compared with alkylated Y6 (ε_r = 3.36), asymmetric glycolated Y6-4O shows a notably higher ε_r value of 5.13 and better solubility in nonhalogen solvents. Because of the higher ε_r value, the devices based on as-cast PM6:Y6-4O processed using toluene exhibit a higher charge separation yield, slower bimolecular recombination kinetics, and less voltage loss relative to the control devices based on PM6:Y6. Consequently, a high PCE of 15.2% is achieved for PM6:Y6-4O-based devices, whereas the PM6:Y6-based devices show PCEs of only 7.38%. 15.2% is the highest PCE for the as-cast nonhalogenated processed OSC devices, and it is also much higher than the values ( 5) organic photovoltaic semiconductors.