The photoconductivities of a series of novel polyacetylene derivatives (PAs) serving as charge generation materials in the single-layered photoreceptors were investigated using photoinduced xerographic discharge technique. It was found that the substitution can improve the photosensitivity of PAs by increasing the conjugation of π electrons. When the substituent is itself photoconductive, the photoconductivity becomes even higher. It can be concluded from cyclic voltammetry that when the HOMO level of the polymer is closer to that of the charge transport material, the photoconduction performance will be better.