Aerospace white paint has excellent properties and can be sprayed in satellite antenna and other large spacecraft surfaces, while UV irradiation has important influence on the properties of it. The UV irradiation effect on the electrical properties of AEROSPACE white paint is studied firstly in this paper, and then the changing mechanism of it is discussed by the aid of XPS. It was found that ZnO in AEROSPACE white paint decomposes in ultraviolet irradiation and the color of AEROSPACE white paint turns to light yellow. The surface resistivity of AEROSPACE white paint decreases with near ultraviolet irradiation, and has back effect in some extent when it returns to atmosphere. Decomposition of ZnO, decrease of adsorbed to Oxygen and increase of oxygen vacancy are the origin of decrease of surface resistivity of AEROSPACE white paint under near ultraviolet radiation.