During the operation of multi-electric aircraft, the polytetrafluoroethylene (PTFE) material used to insulate the aviation cable is subjected to a high electric field while working under the extreme conditions of high temperatures for a long time, which can easily cause a partial discharge and even flashover along the surface, which seriously threaten the safe operation of the aircraft. In this paper, the electrical insulation properties of PTFE were regulated via modification by the magnetron sputtering of TiO2 under high temperatures, and modified PTFE with different sputtering times was prepared. The direct current (DC) surface discharge, surface flashover, and electric aging characteristics of modified PTFE were studied under the condition of 20~200 °C, and the mechanisms by which modification by sputtering of TiO2 and high temperature influence the insulation properties were analyzed. The results show that the surface discharge intensity increases with the increase in temperature, the modification by sputtering of TiO2 can significantly inhibit the partial discharge of PTFE, and the flashover voltage first increases and then decreases with the increase in the modification time. The modification by magnetron sputtering can effectively increase the surface potential decay rate of the PTFE, increase the shallow trap energy density, effectively avoid charge accumulation, inhibit the partial discharge phenomenon, and improve the surface electrical insulation and anti-aging properties.