Dielectric energy storage capacitors have advantages such as ultra-high power density, extremely fast charge and discharge speed, long service lifespan and are significant for pulsed power system, smart power grid, and power electronics. Polypropylene (PP) is one of the most widely used dielectric materials for dielectric energy storage capacitors. It is of interest to investigate how to improve its electrical breakdown strength by nanodoping and the influencing mechanism of nanodoping on the electrical breakdown properties of polymer nanocomposites. PP/Al2O3 nanocomposite dielectric materials with various weight fraction of nanoparticles are fabricated by melt-blending and hot-pressing methods. Thermally stimulated current, surface potential decay, and dc electrical breakdown experiments show that deep trap properties and associated molecular chain motion are changed by incorporating nanofillers into polymer matrix, resulting in the variations in conductivity and dc electrical breakdown field of nanocomposite dielectrics. Then, a charge transport and molecular displacement modulated electrical breakdown model is utilized to simulate the dc electrical breakdown behavior. It is found that isolated interfacial regions formed in nanocomposite dielectrics at relatively low loadings reduce the effective carrier mobility and strengthen the interaction between molecular chains, hindering the transport of charges and the displacement of molecular chains with occupied deep traps. Accordingly, the electrical breakdown strength is enhanced at relatively low loadings. Interfacial regions may overlap in nanocomposite dielectrics at relatively high loadings so that the effective carrier mobility decreases and the interaction between molecular chains may be weakened. Consequently, the molecular motion is accelerated by electric force, leading to the decrease in electrical breakdown strength. The experiments and simulations reveals that the influence of nanodoping on dc electrical breakdown properties may origin from the changes in the charge transport and molecular displacement characteristics caused by interfacial regions in nanocomposite dielectrics.