The Raman scattering analysis of S-rich CuIn(S,Se)(2) layers produced by electrodeposition of CuInSe2 precursors and annealing under sulphurising conditions shows the strong dependence of their crystalline quality on the annealing parameters. Worsening of the crystalline quality is reflected by the presence of an increasing contribution at the higher frequency side of the main Raman band. The comparison of these data with the solar cell parameters points out the existence of a correlation between the efficiency of the devices and the width of the mode. The dependence of the Raman spectra on differences in the process parameters with significant impact in the microcrystalline quality of the layers give interest to the use of Raman scattering as process assessment technique for device quality control. (c) 2007 Elsevier B.V. All rights reserved.