Electrostatic capacitors with ultrahigh power density are the key components in modern electrical and electronic systems. Polymers are preferred dielectrics for high-voltage electrostatic capacitors, however, unable to meet the ever-growing high-temperature requirements in emerging applications, such as electric vehicles, and photovoltaic power generation. In this work, sandwich-structured Polyphenylene sulfide (PPS) films with Al2O3 as the coating layer have been prepared by using roll-to-roll magnetron sputtering. The incorporation of Al2O3 coating layers enhances the potential barrier height at the electrode/dielectric interface, thereby impeding charge injection from electrodes and suppressing high-temperature electrical conduction. Consequently, the sandwich-structured PPS films demonstrate significantly improved breakdown strengths and enhanced capacitive performance at elevated temperatures compared to neat PPS films. The roll-to-roll magnetron sputtering process employed in fabricating these sandwich-structured dielectric films is highly compatible with large-scale capacitor film production. Thus, sandwich-structured PPS films hold promise in addressing the challenge of scalable fabrication of high-performance, high-quality polymer films required for high-temperature capacitive energy storage.