Monolayers of unsubstituted copper phthalocyanine (CuPc) were prepared on a water surface by spreading a solution of CuPc in dichloromethane containing trifluoroacetic acid, and were deposited as multilayer films by means of a horizontal lifting method. A preferential orientation of CuPc molecules in the films was indicated from polarized absorption spectra and X-ray diffraction patterns. It was shown that a CuPc monolayer on the water surface consists of two-dimensional microcrystals.