In this paper, hierarchical structure design method is proposed for improving the dielectric performance of polypropylene (PP) for metallized film capacitors. The results show that the composite film with 0.02 wt% terephthalaldehyde doping and functional layer thickness occupying 25% shows the best dielectric properties. The leakage conductivity declines by 89.0%–94.3%, the DC breakdown strength grows by 15.6%–19.7% and the discharged energy density improves by 50.6%–53.4%. Terephthalaldehyde doping introduces sites that could capture free holes, thereby blocking the carrier migration path. The hierarchical structure design results in the holes accumulating in the functional layer and the reverse electric field formed suppresses the charge injection from the anode. Furthermore, the probability of intrinsic charge excitation due to the band gap width reduction is greatly reduced. The method provides a reference for improving the dielectric performance of PP films from the perspective of regulating the charge transmission behavior.