Titanium was electrodeposited from a nominal 0.24M TiCl4 in 1-methyl-3-butyl-imidazolium bis (trifluoro methyl sulfone) imide ([BMIm]BTA) at room temperature on a Au(1 1 1) substrate. The process of electrodeposition was studied by cyclic voltammetry, chrono amperometry and in situ scanning tunneling microscopy (STM). In a first step TiCl4 is reacted to TiCl2, which is subsequently reduced to metallic Ti. Two dimensional (2D) clusters form preferentially on the terraces in the under potential deposition range. 2D clusters presumably of TiCl3 precipitates grow and coalesce to cover the whole substrate with a 2D film at a substrate potential below -1.1 V versus ferricenium/ferrocene ([Fc](+)/[Fc]) redox couple. At a potential of -1.8 V a dense layer of three dimensional (3D) clusters of titanium of 1-2 nm thickness is formed. The features of the I-U tunneling spectra and the relative reduction of the effective tunneling barrier by 0.8 eV with respect to gold clearly indicate the metallic character of Ti deposits. Observation of circular holes on the Au(1 1 1) substrate after dissolution of the deposited Ti indicates the formation of Au-Ti surface alloying. (C) 2004 Elsevier Ltd. All rights reserved.