Regulated triboelectrification has attracted considerable research attention due to its potential applications in harvesting energy and importance in antistatic protection. Irradiation is an effective and stable modification method due to its adjustable and uniform irradiation parameters. Moreover, atomic oxygen (AO) irradiation is an important component in low earth orbit, which is a considerable factor for promoting triboelectric nanogenerators (TENGs) in outer space. AO irradiation was utilized to manipulate surface structure and chemical composition to regulate electrical properties. AO irradiation can increase electron-donating groups and enhance electric positivity of PDMS films due to the transition from Si–C bonds to Si–O bonds. Therefore, different trends of PTFE and PS were caused by their TENG composition with irradiated PDMS. Tribocharge crossover polarity and charge generation were prevented completely in PS@PDMS TENGs by adjusting irradiation time to 4.1 h. Short-circuit current enhanced from 5 μA to 22 μA and output voltage increased from 160 V to 760 V when PDMS films in PTFE@PDMS TENGs were subjected to AO irradiation for 6 h. This study demonstrated that AO irradiation can manipulate triboelectric properties of silica-based materials, which are potential components for harvesting energy and preventing electrostatic hazard in outer space.