Polyvinyl chloride (PVC) and sodium aside were reacted to synthesize PVC-azide, photosensitive polymer, the photosensitive characteristics of which were investigated by yield of residual film and I.R. Spectrum. PVC-azide, 42.01% conversion of chlorine, was prepared by the reaction of 0.2 mole of PVC with 0.1 mole of sodium azide at 60$^{circ}C$ for 5 hours. 5-nitroacenaphthene, acetophenone and benzophenone were used as a sensitizer. When PVC-azide was irradated for 8 and 16 min. with the addition of 3% of the above three sensitizers, it was observed that the effect of sinsitizer is as follows; 5-nitroacenaphthene> acetophenone> benzophenone and the best result was obtained when the 5-nitroacenaphthene, acetophenone and benzophenone was 3%, 5%, and 8% respectively. The less the weight of film Per area, the better the yield of residual film. The characteristic peak (2,100cm-1) of PVC-azide by ultraviolet irradiation was strikingly decreased.