The molecular orientations of hexadecafluorophthalocyanatozinc (F16ZnPc) vacuum-deposited on An and Mg substrates were studied by near edge X-ray absorption fine structure (NEXAFS) spectroscopy and infrared reflection-absorption spectroscopy. The molecular planes of F16ZnPc deposited on An and Mg substrates were found to be nearly parallel and vertical to the substrate surface, respectively, from the polarization dependence of NEXAFS spectral intensity. The air-exposure of the metal substrate before F16ZnPc deposition affected the molecular orientation on Au, while little effect was found for the Mg substrate. These results are discussed in terms of the molecule molecule and molecule-substrate interactions. (c) 2005 Elsevier B.V. All rights reserved.