A dual-layered photoreceptor device made from a χ-form metal-free phthalocyanine (χ-H 2 Pc) was prepared. The effects of impurity sulfur and its chemical valence state in the χ-H 2 Pc on the properties of electrophotography have been studied. One of the interesting phenomena observed is the role of impurity of sulfur in χ-H 2 Pc is promoting the performance of photoreceptor devices. That is, the higher the sulfur impurity in χ-H 2 Pc, the lower the surface residual potential on photoreceptor devices, suggesting that it would be a kind of defect assisted carrier injection from the carrier generation layer (CGL) into the carrier transport layer (CTL) and followed by the trap modulated carrier transport.The photoelectron properties of a dual-layered photoreceptor device were characterized by corona charging/photodischarging measurements. They are the saturated initial surface dark potential (V 0 ), dark decay rate DR(%)=(V D /V 0 )x100% measured by the average potential decreases in the initial 2s after dark decay, V D is measured after 2s dark decay, light sensitivity (E 1 / 2 =E L xt 1 / 2 ) calculated from illuminating power (E L ) and half photodecay time (t 1 / 2 ), and photodecay surface residual potential (V r ) after 1.5s illumination.