The capacitive energy storage of polymer dielectrics degrades rapidly at elevated temperatures and electric fields owing to the exponential growth of conduction loss. The formation of conduction loss is mainly attributed to the transport of charge carriers in polymer dielectrics and at the dielectric/electrode interface, which is dominated by bulk-limited and electrode-limited conduction mechanisms, respectively. Establishing a strong electrostatic interaction between guest charge carriers and host polymer dielectrics has been extensively employed to inhibit charge transport. The electrostatic interaction mainly consists of electrostatic attraction and repulsion. The construction of electrostatic attraction can be implemented by introducing deep traps in polymer dielectrics to capture the charge carriers and restrain their transport. On the contrary, the electrostatic repulsion is based on the scattering effect of the electrons-rich surface, which can effectively reduce the mobility of energetic electrons and change the path of charge transport. Unfortunately, a systematic summary of using electrostatic interaction to regulate charge transport is still lacking. In this review, we critically analyze the electrical conduction mechanisms in polymer dielectrics and summarize the recent advances in the regulation of high-temperature capacitive energy storage performance by employing electrostatic attraction and repulsion, among which the advantages and limitations are also discussed. This review is concluded by highlighting the challenges and future opportunities.