Epoxy resin composites are widely used as insulating and supporting materials in high-voltage power systems due to their excellent mechanical and electrical properties. However, long-term operation under high-voltage direct current (HVDC) induces surface flashover. Plasma enhanced chemical vapor deposition (PECVD) has been shown to effectively improve the surface insulation properties of epoxy resin. However, the influence of substrate temperature on the film composition, stress, morphology, and surface flashover performance remains unclear. This study uses PECVD to treat epoxy resin, enhancing its surface flashover performance. Tetraethoxysilane (TEOS) is used as the precursor to deposit nano-scale SiOx films on the epoxy resin surface. The effects of different substrate temperatures on the surface flashover voltage, physicochemical properties, and mechanical properties of epoxy resin are characterized. The results show that the surface flashover voltage increases and then saturates with increasing substrate temperature, improving by 27.4% at 60°C compared to untreated samples. The surface roughness of epoxy resin decreases after plasma deposition, while highly oxidized silicon-containing functional groups are introduced. When the substrate temperature increases from 20°C to 60°C, the interfacial bonding strength improves by 25.9%. This study provides a simple, efficient, and controllable method to enhance the surface flashover performance of epoxy resin, promoting the application of this technology in engineering practice.