In this work, we develop amorphous Carbon (a-C) films, free of hydrogen and hydrogenated, on rigid and flexible substrates by magnetron sputtering. The morphology of the a-C/polymeric and carbon multilayer systems is studied at the nanoscale to meet the requirements of emerging applications in packaging and protective overcoats. Surface-sensitive characterization techniques were used: (i) Spectroscopic Ellipsometry, detecting the variation of the polarization state of light in reflection from the a-C film, (ii) nanoindentation techniques, (iii) Scanning probe microscopies. We investigate the variations in the surface and interface morphology, elemental composition, microstructure, optical, nanomechanical and functional properties of the films grown on the various substrates and we identify the differences on the mechanism of carbon growth and discuss their effect on their mechanical and functional behavior. (c) 2004 Elsevier B.V All rights reserved.