Controlled reduction by hydrogen, of the equivalent five monolayer of MoO3 deposited on TiO2 as a function of the reduction temperature up to 873 K, enabled us to obtain three Mo2O5, bifunctional (metal-acid) MoO2(H-x)(ac) and the metallic Mo(0) phases. Characterization of these phases was made by employing surface XPS-UPS techniques in parallel with catalytic reactions. Hydroisomerization of n-hexane occurs on the bifunctional phase, while hydrogenation/ dehydrogenation and benzene formation were performed by the metallic Mo state.