Commercial biaxially oriented polypropylene (BOPP) film capacitors have been widely applied in the fields of electrical and electronic engineering. However, due to the sharp increase in electrical conduction loss as the temperature rises, the energy storage performance of BOPP films seriously degrades at elevated temperatures. In this study, the grafting modification method is facile and suitable for large-scale industrial manufacturing and has been proposed to increase the high-temperature energy storage performance of commercial BOPP films for the first time. Specifically, acrylic acid (AA) as a polar organic molecular is used to graft onto the surface of commercial BOPP films by using ultraviolet irradiation (abbreviated as BOPP−AA). The results demonstrate that the AA grafting modification not only slightly increases the dielectric constant, but also significantly reduces the leakage current density at high-temperature, greatly improving the high-temperature energy storage performance. The modified BOPP−AA films display a discharged energy density of 1.32 J/cm³ with an efficiency of >90% at 370 kV/mm and 125 °C, which is 474% higher than that of the pristine BOPP films. This work manifests that utilizing ultraviolet grafting modification is a very efficient way to improve the high-temperature energy storage performance of commercial BOPP films as well as provides a hitherto unexplored opportunity for large-scalable production applications.