Nb-containing siliceous porous clay heterostructure (PCH) (Nb-content from 0 to 30 wt%), prepared from a bentonite, has been used as effective support in the preparation of supported NiO catalysts (with NiO loading from 15 to 80 wt%). Supports and NiOcontaining catalysts have been characterized by several physicochemical techniques, and tested in the oxidative dehydrogenation of ethane. The characterization results on Nbcontaining supports show the presence of well-anchored Nb 5+ species, without the formation of Nb2O5 crystals. A high dispersion of nickel oxide (which presents a low crystallinity) has been observed when using the Nb-containing PCH supports. In addition, when NiO is supported on these Nb-containing porous clays, it displays a higher effectiveness in the ODH of ethane (ethylene selectivity of ca. 90 %) than NiO supported on the corresponding Nb-free siliceous PCH or on Nb2O5 (ethylene selectivity of ca. 30 and 60 %, respectively). Factors such as the NiO-Nb 5+ interaction, NiO particle size and the properties of surface Ni n+ species have shown to be determining for the catalytic performance.