A novel polymer with quasi-one-dimensional structure of ethylenediamine bridged polymeric manganese phthalocyanine [PcMn(eda)](n) was synthesized by complexing of manganese phthalocyanine (MnPc) and ethylenediamine (eda). The structure of the polymer was identified by infrared, ultraviolet-visible, and differential scanning calorimetric analysis. It was found that the polymer [PcMn(eda)](n) showed much better photoconductive property than MnPc monomer when [PcMn(eda)](n) or MnPc was used as the charge-generation material (CGM)-matched hydrazone charge-transportation material (CTM). Furthermore, the photoconductivities of [PcMn(eda)](n) and MnPc were improved if the charge-generation layers (CGLs) were made by electric field poling. All these observations are ascribed to the effects of the one-dimensional molecular structure and the ordered material structure, respectively.