The first part of present paper described the synthesis procedure for the preparation of VOx/ZrO2 catalysts with fibrous morphology. In the present contribution, the same procedure is applied for the preparation of multi-metallic catalysts, such as V-Mo-O/ZrO2 and V-Nb-O/ZrO2. In all the cases, and in only one step, the multi-metallic porous fibers were obtained. The characterization data has shown that the segregation of metal atoms is adequate, avoiding the formation of oxides such as V2O5, Nb2O5 and/or Mo2O3, and the activity under the propane ODH reaction of VOx based catalysts is improved by the addition of Mo.