Tungstated oxides were prepared from several supports and characterized. The tungsten surface repartition and availability depends on the initial support. The acidity in water was evaluated through a model compound reaction, cyclohexanol dehydration. The results show that acidity in water is completely different from gas phase acidity (from NH3-TPD), evidencing the crucial role of water in the acid catalytic activity. The tungstated oxides were then mixed with Pt/ZrO2 to obtain a bifunctional catalytic system, which was used for transforming sorbitol in water. The activity and selectivity is highly dependent on the acid phase. TiO2-WOx led to increased activity and higher selectivity for long chain hydrocarbons (C5-C6 alkanes) which can be valorized as biofuels, when compared to traditional sorbitol transformation catalyst. Al2O3-WOx is not acid in water but produces short alcohols by C-C cleavage. These results provide an incentive for further catalysts preparation.