Copper tetra-(octyl-alkoxy-carbonyl)-phthalocyanine (CuPc-C8) and 3,4,9,10-tetra-(octyl-alkoxy-carbonyl)perylene (Pery-C8) attached with long alkyl chains by covalent bonds were synthesized. Both of the two compounds showed good solubility in organic solvents, and the compatibility between them was improved. The novel composite of CuPc-C8/Pery-C8 was prepared by the solution-blending method. Atomic force microscopy (AFM) demonstrated the formation of the bulk heterojunction structure in their cast-coated films. Enhanced photosensitivity was observed in the photoreceptor made from the CuPc-C8/Pery-C8 composite, which was interpreted in terms of the large interfacial area between the two components due to the existence of the bulk heterojunction structure.