The friction characteristics of two-dimensional materials in the ultraviolet (UV) radiation environment are important to the reliability of two-dimensional material nano-structures of space equipment. A novel mechanism of UV light-sensitive nano-friction on graphene was proposed by ultraviolet vacuum irradiation modification using an atomic force microscope (AFM). The surface roughness, adhesion force, and friction of graphene were gradually reduced over a time of irradiation below 3 min. UV185 passes through graphene and causes photochemical reactions between its bottom layer and Si/SiO₂ substrate, resulting in hydroxyl, carboxyl, and silanol suspension bonds and sp3-like bonds, which enhances the binding energy of graphene on the substrate and inhibits the out-of-plane deformation resulting in roughness and friction reduction. However, as the irradiation time increased to 5 min, the friction force increased rapidly with the aging effect and the breakdown of sp3-like bonds between the graphene–substrate interface. This study presents a new method of controlling nanofriction on graphene based on UV irradiation-sensitive posterities in vacuum conditions, which is essential to the application of two-dimensional materials in aerospace equipment, to improve anti-aging properties and wear reduction.