Biaxially stretched poly (p‐phenylene sulfide) (PPS) film showed high photosensitivity after being annealed in oxygen for 6 h at a temperature between 270 and 285 °C. The spectral dependence of xerographic photosensitivity of the film had a peak at around 365 nm, and xerographic gain under 365‐nm UV irradiation was 0.1 or above. The micro‐Vickers hardness of PPS reached 60 kg/mm2after annealing at 280 °C for 6 h. The spectral photosensitivity was greatly improved by depositing a thin amorphous selenium‐tellurium alloy on the annealed PPS film. The half‐decay exposure of the annealed PPS with Se‐Te alloy film was 2.3 lx s under white illumination. These experimental results demonstrate that the annealing of PPS film under an oxygen environment gives this film excellent photosensitivity and mechanical durability and hence, renders this material attractive for a xerographic application.