Surface modification of PMMA(polymethylmethacrylate) was carried out by irradiation of low energy ion and/or electron, which is expected to improve the surface hardness by introduction of a thin modified layer. Surface hardness was measured by using the nanoindentation test. To clarify the structure and the properties of the modified layer, depth profiles of composition and chemical bonds were analyzed using XPS(X-ray photoelectron spectroscopy). Forming cross-linking structure that contributed to the surface hardness was analyzed using dyeing method.From these results, it was confirmed that surface hardness increased and existence of cross-linking structure. It was suggested that the existence of the structure brought about the increase of surface hardness, and showed the utility of the dyeing method.