Surface flashover is an inevitable insulation issue for basin-type insulators in gas-insulated switchgears/lines, which significantly challenges the reliability of the electrical power systems. Previous studies have indicated that polymer/semiconductor-filler composite coatings effectively improve the insulation properties; however, the influence mechanism of the coating materials on flashover has not been demonstrated from a molecular perspective. In this work, epoxy/silicon-carbide (EP/SiC) composites were coated onto an EP substrate. The energy-level structure, surface trap, surface charging, and DC flashover voltage in SF6/N2 were calculated and characterized, and the process by which the tailored molecular energy level influences surface charge transport and flashover characteristics was elucidated. The incorporating of SiC particles reduced the width of the bandgap and introduced shallow traps, which improved carrier mobility and surface conductivity. Quantitative analysis of charge transport indicated that the improved carrier mobility and reduced surface trap level accelerated the surface charge dissipation. This reduced the tangential electrical field distortion and surface charge density and further impeded gas ionization. When the SiC concentration was 15 wt%, the flashover performance improved by 20.88%. This study describes the mechanism by which the EP/SiC coating regulates the surface charge distribution to improve the surface flashover performance by establishing a relationship among the microscopic molecular energy-level structures, mesoscopic charge transport, and macroscopic discharge phenomena.