With the aim of obtaining materials with properties for use as catalysts, two new trimetallic oxides containing Co or Ni and Mo and W were synthesized by a hydrothermal method, using milder conditions than those normally used for wolframite type solids. They were characterized by X-ray diffraction, Fourier transformed infrared spectroscopy, laser Raman spectroscopy, temperature-programmed reduction and atomic absorption spectroscopy, indicating that pure wolframite phases were formed. The X-ray diffraction studies confirmed the formation of the structure in the monoclinic system with cell parameters similar to nickel tungsten wolframite. The laser Raman and infrared spectra showed differences among the samples, mainly due to the incorporation of molybdenum atoms in the wolframite structure. Incorporation of molybdenum in the catalysts improved catalytic activity for propane oxidative dehydrogenation, and lower reaction temperatures were required in order to obtain similar propene yields as in bimetallic tungsten wolframites.