The change in micro-wear of polymers, especially a silicone rubber after vacuum ultraviolet(VUV) irradiation at the wavelength of 147 nm, was studied by means of AFM in scratching mode. It was found that the effect of VUV irradiation on polymer surface micro-wear was related to the extent of crosslinking, strongly depending on the chemical structure of polymers and irradiation conditions. The VUV treatment both in the presence of air and in vacuum resulted in a significant decrease in the micro-wear of silicone. In addition, VUV irradiation made the siloxane smoother, characterized by about a three-fold decrease in the average roughness. ESCA spectra revealed that the improvement in the micro-wear of silicone by VUV irradiation in vacuum (0.05 torr) and VUV photooxidation in air (2.5 torr) was associated with the formation of two different types of crosslinks via CH2 groups and O atoms, respectively.