Electrodeposition of Si on substrates such as Ni, Ag and GC from acetonitrile and tetrahydrofuran containing SiCl4 and SiHCl3 as precursors is reported. The deposits readily oxidize on exposure to air but XPS analysis of a deposit with minimum contact with air confirms that elemental Si (2p, 99.5 eV) is electrodeposited. The deposits contained C, O, N and Cl impurities; annealing under argon improved the quality of the deposits. Studies related to initial stages of Si growth using cyclic voltammetry and chronoamperometry suggest that growth occurs via four stages (1) nucleation and localized growth, (2) growth in between islands, (3) growth inhibition and (4) slow growth stage and the growth is inhibited after a layer (similar to 2 nm) of Si is electrodeposited on the substrate. (C) 2010 Elsevier Ltd. All rights reserved.