Alkali treatment of titanium with subsequent heat treatment has been adapted as an important pre-treatment procedure for hydroxyapatite formation in orthopaedic applications. The electrochemical study during the alkali treatment process has not been explored yet. In the present work, electrochemical impedance spectroscopic (EIS) studies have been employed to analyse the electrochemical behaviour of titanium during the alkali treatment. The open circuit potential and potentiodynamic polarisation measurements were carried out in simulated body fluid (SBF) solution. Scanning electron microscopy and energy dispersive X-ray analysis were used to characterize the surface morphology and to correlate the results obtained from the electrochemical studies. An optimum growth of the passive film was found to occur at the end of 17th hour of treatment by alkali treatment. The alkali treated titanium immersed in SBF solution for various durations exhibited the formation of a duplex layer structure due to an inner barrier layer and an outer gel layer during the initial periods of immersion. However, with increase in immersion time to 10 days, a stable apatite layer was formed over the barrier layer and this was confirmed from the equivalent circuit fitted for the impedance data. (c) 2007 Elsevier Ltd. All rights reserved.