The tribological performances of perfluoroalkylpolyethers (PFPE) with graphene (Gr), WS2, and the mixture of Gr and WS2 (Gr+WS2) before and after ultraviolet (UV), atomic oxygen (AO), and proton (Pr) irradiations were investigated. The composition and structure of PFPE, Gr, WS2, and Gr+WS2 were also analyzed to understand the effects of irradiation on the tribological behaviors of PFPE with additives. The results indicated that serious deterioration and degradation of PFPE took place and Gr was transformed to amorphous carbon after Pr irradiation, and surface oxidation of WS2 occurred under the irradiations of AO and Pr. Moreover, compared to PFPE and PFPE additized with Gr and WS2, PFPE with the addition of Gr+WS2 exhibited excellent friction and wear reduction before and after UV and AO irradiations.