Single step electrodeposition (ED) of Se-rich CuInSe2 precursors, followed by RTP annealing under sulphurising conditions leading to S-rich CuIn(S,Se)(2) films, constitutes a promising technology for low cost high efficiency solar cells. In this work, a Raman scattering (RS) analysis of Se rich precursors grown under ED conditions leading to different chemical compositions is reported. RS has allowed identification of the main secondary phases in these layers with elemental Se, Cu-Se binary and ordered vacancy compound (OVC) phases. The experimental data show a strong dependence of the spectral contributions related to Se and Cu-Se with the layer molecularity, and the formation of these phases is mainly determined by the content of excess Se in the layers. The correlation of these data with the characteristics of the solar cells fabricated with these precursors, shows the strong impact of the presence of the Cu-Se phase on the performance of the final devices. These results point out the key role played by this binary phase on the formation of secondary phases after the sulphurising step. (C) 2008 Elsevier B.V. All rights reserved.