The molecular structure of polytetrafluoroethylene (PTFE) coatings deposited on aluminium substrates was investigated by the method of attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR). It has been shown experimentally that PTFE coatings deposited by the electron-beam dispersion method have molecular orientation and are ordered nonmonotonously during the process of coating growth. Maximum order and orientation of molecules along the normal to the substrate are observed in an interfacial layer located within up to 100 nm to the substrate. The observed morphological and orientation features of the formed layers were explained using the proposed adsorption-diffusion mechanism of polymer coating formation. (C) 2009 Elsevier B.V. All rights reserved.