Poly (Vinyl Chloride-Co-Isobutyl Vinyl Ether) (PVCCIVE) with rutile and anatase nano-TiO2 was investigated with XPS before and after UV light exposure respectively. The results indicate that the elements such as Chlorine and Oxygen in the PVCCIVE resin are rich in the surface, namely skin effect, in contrast, Titanium and Carbon are rich in the inner. Meanwhile, the smaller the pigment particles, the higher the content in the surface. The results also show that the rutile nano-TiO2 is excellent in UV screening and reduces the ageing of resin, while the anatase nano-TiO2 is highly active in photo catalysis and accelerates the ageing of resin. Hence then, rutile nano-TiO2 is a kind of promising UV absorber.