As a key insulating material in power equipment, epoxy resins (EP) are often limited in practical applications due to space charge accumulation and mechanical degradation. This study systematically investigates the effects of SiO₂ nanoparticle doping on the electrical and mechanical properties of SiO₂/EP composites through molecular dynamics simulations and first-principles calculations. The results demonstrate that SiO₂ doping enhances the mechanical properties of EP, with notable improvements in Young’s modulus, bulk modulus, and shear modulus, while maintaining excellent thermal stability across different temperatures. Further investigations reveal that SiO₂ doping effectively modulates the interfacial charge behavior between EP and metals (Cu/Fe) by introducing shallow defect states and reconstructing interfacial dipoles. Density of states analysis indicates the formation of localized defect states at the interface in doped systems, which dominate the defect-assisted hopping mechanism for charge transport and suppress space charge accumulation. Potential distribution calculations show that doping reduces the average potential of EP (1 eV for Cu layer and 1.09 eV for Fe layer) while simultaneously influencing the potential distribution near the polymer–metal interface, thereby optimizing the interfacial charge injection barrier. Specifically, the hole barrier at the maximum valence band (VBM) after doping significantly increased, rising from the initial values of 0.448 eV (Cu interface) and 0.349 eV (Fe interface) to 104.02% and 209.46%, respectively. These findings provide a theoretical foundation for designing high-performance epoxy-based composites with both enhanced mechanical properties and controllable interfacial charge behavior.