A new generation of Ni-Sn-O, Ni-Ti-O, and Ni-W-O catalysts has been prepared by a solid state grinding method. In each case the doping metal varied from 2.5% to 20%. These catalysts exhibited higher activity and selectivity for ethane oxidative dehydrogenation (ODH) than conventionally prepared mixed oxides. Detailed characterisation was achieved using XRD, N2 adsorption, H2-TPR, SEM, TEM, and HAADF-STEM in order to study the detailed atomic structure and textural properties of the synthesized catalysts. Two kinds of typical structures are found in these mixed oxides, which are (major) “NixMyO” (M = Sn, Ti or W) solid solution phases (NiO crystalline structure with doping atom incorporated in the lattice) and (minor) secondary phases (SnO2, TiO2 or WO3). The secondary phase exists as a thin layer around small “NixMyO” particles, lowering the aggregation of nanoparticles during the synthesis. DFT calculations on the formation energies of M-doped NiO structures (M = Sn, Ti, W) clearly confirm the thermodynamic feasibility of incorporating these doping metals into NiO struture. The incorporation of doping metals into the NiO lattice decreases the number of holes (h+) localized on lattice oxygen (O2- + h+ ➔ O●-), which is the main reason for the improved catalytic performance (O●- is known to favor complete ethane oxidation to CO2). The high efficiency of ethylene production achieved in these particularly prepared mixed oxide catalysts indicates that the solid grinding method could serve as a general and practical approach for the preparation of doped NiO based catalysts.