In the direct current electric field, the surface of epoxy resin (EP) insulating material is prone to charge accumulation, which leads to electric field distortion and damages the overall insulation of the equipment. Nano-doping is an effective method to improve the surface insulation strength and DC flashover voltage of epoxy resin composites. In this study, pure bismuth ferrite nanoparticles (BFO), as well as BFO nanofillers, which were doped by La element, Cr element as well as co-doped by La + Cr element, were prepared by the sol-gel method. Epoxy composites with various filler concentrations were prepared by blending nano-fillers with epoxy resin. The morphology and crystal structure of the filler were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) tests. The effects of different filler types and filler mass fraction on the surface flashover voltage, charge dissipation rate, and trap characteristics of epoxy resin composites were studied. The results showed that element doping with bismuth ferrite nanofillers could further increase the flash voltage of the composites. The flashover voltage of La + Cr elements co-doped composites with the filler mass fraction of 4 wt% was 45.2% higher than that of pure epoxy resin. Through data comparison, it is found that the surface charge dissipation rate is not the only determinant of the flashover voltage. Appropriately reducing the surface charge dissipation rate of epoxy resin composites can increase the flashover voltage. Finally, combining with the distribution characteristics of the traps on the surface of the materials to explain the mechanism, it is found that the doping of La element and Cr element can increase the energy level depth and density of the deep traps of the composite materials, which can effectively improve the flashover voltage along the surface of the epoxy resin.