X-ray photoelectron and Raman spectroscopies were used to investigate the chemical and the structural properties of thin diamond films synthesised by Plasma Assisted Chemical Vapour Deposition (PACVD). Continuous polycrystalline diamond films were grown under different plasma conditions and based on the combination of detailed XPS and Raman spectroscopic analysis two main topics are highlighted (i) the stress measurements were discussed by distinguishing clearly the chemical effects from the mechanical effects; (ii) an electronic gap at 2.7 eV probed by Raman resonance that corresponds to an energy loss peak on the XPS carbon signal, was related to the surface hydrogenation. (c) 2008 Elsevier B.V. All rights reserved.