2,3,7,8,12,13,17,18-Octakis(methylthio)-5,10,15,20-21H,23H-porphyrazine, H(2)OMTPz, was used for the preparation of thin films by the Langmuir-Shafer technique. The related analysis of the floating layer on the water surface has revealed the existence of large and randomly oriented three-dimensional aggregates, investigated by Brewster angle microscopy and by UV-vis reflection spectroscopy. The transfer of the floating layer onto the solid hydrophobized substrates (quartz and glass) originated films that on the contrary have exhibited, by UV-vis spectroscopic analysis with polarized light, an average preferential edge-on arrangement of porphyrazine molecules with respect to the support surface. Finally, spectroscopic ellipsometry allowed us to measure the film thickness (consistent with previous data) and optical parameters.