Surface flashover is a destructive high-voltage discharge phenomenon greatly limiting the update of modern power electronic and electrical equipment. Surface plasma treatment is a high-energy, eco-friendly, and convenience method, it changes the surface properties and owns potential to improve flashover voltage. In the present work, plasma fluorination (PF) technique are used to treat EP/Al2O3 composites, surface morphology, element and bonds content, surface trap, conductivity, charging, and DC flashover voltage are tested and simulated, the effects of plasma on surface discharge are explained through the investigation from microscopic molecular reactions to macroscopic flashover characteristics. It indicates the 20 min PF modified sample exhibits the superior DC flashover performance, increasing by 17 % compare to untreated sample. During PF modification, the epoxy chains are degraded and fluorinated, the degradation rather than fluorination of molecular chains introduce large amounts of shallow traps into the composites, accelerating carriers’ migration and improving surface conductivity, causing surface charges to dissipate through surface conductance. Consequently, the surface electric field distortion degree reduces, and the subsequent gas ionization and plasma formation in the gas phase is suppressed, leading to the improvement of DC flashover voltage after PF modifications.