Phthalocyanine multi-layered films, composed of copper phthalocyanine (CuPc) and naphthalene tetracarboxylic dianhydride (NTCDA), were fabricated by an organic molecular beam deposition method. Results from several analyses, like XPS and RHEED, revealed an epitaxial layer-by-layer structure of the multilayers, pointing toward a possible candidate of molecular assembly for future photonics devices.