Nb-TiO2 nanomaterials with hierarchical porosity (macro, meso and micropores) have been successfully synthesized using a simple self-assembly method without the need for a surfactant. Improved textural and structural properties were obtained after incorporation of Nb within a TiO2 framework. High Nb dispersion and Nb-Ti interaction were achieved at the Nb-TiO2 nanomaterial surface. With Nb addition to TiO2, the balance of Lewis to Brønsted acid sites was maintained however the acidity increased in strength. The catalytic transformation of 2-propanol and n-butanol was favoured at very low temperatures with a change in selectivity; the dehydration reaction of alcohols into alkenes was promoted by the increase in acidity of the Nb-TiO2 nanomaterials.