The configuration and photoelectron processes of metal-free phthalocyanine multilayered film have been discussed in detail. And by the study of photodecay surface residual potential, the results obtained are that the initial surface dark potential (Vo) charged from DC corona voltage (-6kV) is -910V, the dark surface potential (Vd) measured atter 2-sec. dark decay is -825V, it is 90.3% of the initial surface dark potential (Vo), the rate of dark decay (DR) calculated from initial surface potential (Vo) and dark surface potential (Vd) is 9.3%, the surface residual potential (Vr) measured after 1.5-sec. illumination is 40V, the light sensitivity (E1/2) calculated from illumtinating power (EL) and the time of half photo-decay (t1/2 ) is 2 lux.sec. These values are in valid values region of laser printers. Indicating that metal-free phthalocyanine used in function separated multi-layered film is an appropriate photogenerator-photoconductor. It would pave a solid road to small-size for copies, especially for laser printers, and much expanded scope of studies and applications in organic photoconductor.