A range of hybrid, SiOCH films were deposited on silicon substrates within a radio frequency plasma reactor using hexamethyldisiloxane (HMDSO) as a precursor. The plasma polymerized films were deposited at various HMDSO/argon/oxygen ratios. The composition and structure, at microscopic and nanoscopic levels, of the deposited films were determined by external reflection and transmission Fourier Transform Infrared (FTIR) spectroscopy as well as by X-Ray Photoelectron Spectroscopy (XPS). The content of carbon and oxygen in films were found to be inversely proportional to each other. XPS results showed that the outermost surface of the deposited films are nanoporous and coexist with microporosity which was revealed by electron microscopy. The structure of deposited coatings is anisotropic as was documented by polarized external reflection FTIR spectroscopy. Several correlations between the film chemical composition, surface structure, and macroscopic properties of the films such as: hydrophobicity and hydrophilicity were established. (c) 2013 Elsevier B.V. All rights reserved.