The angle-resolved ultraviolet photoelectron spectra of ultrathin films of copper phthalocyanine (CuPc) on an MoS2 substrate were measured using synchrotron radiation. The azimuthal angle dependence of the photoelectron intensity was analyzed using independent-atomic-center approximation combined with molecular orbital calculation. The results indicate that CuPc molecules lie flat on the substrate and that the film grows epitaxially with respect to the three equivalent directions of the MoS2 surface.