Surface charge distribution change caused by electrons trapped at defects of a SiO2 surface has been observed by using a mirror electron microscope (MEM) under monochromatized ultraviolet (UV) light irradiation. Scratches on the SiO2 surface on a silicon wafer were formed by mechanically polishing to create spatially distributed defects on the SiO2 surface. Exposure of the SiO2 surface by UV light with energy above 4.25 eV, which is the threshold energy for internal photoemission from silicon to SiO2, produced significant change in the contrast in the MEM images. This contrast change is mainly due to negative charging by the photoexcited electrons trapped at the defects along the scratches. The negative charging changes the curvature of the electrostatic equipotential surface above the scratches from a concave shape to a convex shape; as a result, their contrast in the MEM image becomes reversed. The surface density of the trapped electrons at a typical scratch was roughly estimated to be 1010 cm-2. This result of analysis of the contrast change shows that the MEM can be used for spatially resolved and spectroscopic characterizations of defects relating charge trapping in insulator films in conjunction with a charge-injection technique such as UV irradiation.