Different post-treatment processes involving the use of ammonia and hexamethyldisilazane (HMDS) were explored for application to 351 nm third harmonic generation SiO2 antireflective (3ωSiO2 AR) coatings for high power laser systems prepared by the sol-gel method. According to experimental analysis, the 3ωSiO2 AR coatings that were successively post-treated with ammonia and HMDS at 150°C for 48 h and again heat-treated at 180°C for 2 h (N/H 150 + 180 AR) were relatively better. There were relatively fewer changes in the optical properties of the N/H 150 + 180 AR coating under a humid and polluted environment, and the increase in defect density was slow in high humidity environments. The laser-induced damage threshold of the N/H 150 + 180 AR coating reached 15.83 J/cm2 (355 nm, 6.8 ns), a value that meets the basic requirements of high power laser systems.