Surface flashover is a common breakdown phenomenon on material surfaces for which surface charge migration property, determined by surface composition and molecular chain structure, is crucial. Precise modulation of charge migration property by simple and efficient methods to improve surface flashover voltage is the goal in industry. Here, in-plane molecular chain orientation (MCO) modulation by uniaxial stretching was proposed to achieve this goal and investigate the intrinsic mechanism of charge migration on flashover. Flashover voltage and accompanying leakage current, performed with electrodes oriented at varying angles to the MCO direction, show a consistent trend, which skillfully reveals that the facilitated charge migration is favorable for improving flashover voltage. When the stretching ratio is 3.5, the flashover voltage along the stretching direction (SD) increases by up to 48.7%, while the in-plane minimum flashover voltage remains essentially unchanged with the change in stretching ratio. Molecular chain segment motion properties along different directions further elucidate that the surprising improvement of flashover voltage along SD is primarily due to the MCO that promotes intra-chain charge migration. This work provides a new perspective on anti-flashover modification of polymeric dielectric and will promote the development of surface flashover mechanisms.