The effect of UV irradiation and blending with phthalate and terephthalate plasticizers on the photo-stability of Poly (4-vinyl biphenyl) was studied at different intervals of irradiation time and in presence of air. The increase in irradiation time on the photodegradation of polymer thin films caused a change in the intensity and shape of the fluorescence band. It has been found that the stability of the polymer decreases with the increase of irradiation time, and to increases with the increase of the amount of added phthalate and terephthalate plasticizers, which is evidence of polymer photodegradation.The FT-IR spectra of irradiated pure and blended polymer with phthalate and terephthalate plasticizers showed a decrease in some absorption bands and increase in the other bands, this is also another factor for the occurrence of photo degradation of the irradiated polymer. The increase in the intensity of absorption of carbonyl and hydroxyl region, indicates a possible photogegradation of polymeric chains and the formation of alcohols, aliphatic ketones and to the increase in the number of (C=C) that resulted from hydrogen abstraction during chains-scission.