The initial growth stages of materials non-active to a substrate has been extensively studied for decades, whereas there had been fewer studies on the initial growth of active metals on silicon substrate, despite its technological importance. In this paper the very early growth stages of transition metal (Ti, V and Nb) films deposited by rf sputtering on unheated (100) Si substrate were studied by in situ X-ray photoelectron spectroscopy. The following sequence of the phase composition and the growth mechanism changes during deposition process was revealed. Initially in a submonolayer regime, small 3D TiO2 islands are formed via reduction of a native silicon oxide layer on a substrate followed by formation of a TiO phase between TiO2 islands and on their top. After deposition of ca. 2 monolayers a metallic Ti phase appears and later only the metal Ti film grows. The same growth behavior takes place at Nb and V deposition with a difference that in the case of Nb the above changes occur at earlier stages what can be explained by the highest niobium activity to the reduction of silicon oxide in the row V, Nb, Ti. (C) 2006 Elsevier B.V. All rights reserved.