V-Zr-O submicron diameter fibers have been prepared by electrospinning of V and Zr containing solutions in only one calcination step. This is a simple and versatile synthesis method, easy to scale up, that produces porous solids, with fibrous morphology and with VOx catalytically active species, being these solids attractive for alkane partial oxidation reactions, since the catalysts with fibrous morphology present several advantages with respect powered ones. With the new proposed method, at low vanadium loadings (V% w/w < 6.4), surface dispersed VOx were found in the zirconia fiber as shown by Raman spectroscopy analysis, whereas crystalline ZrV2O7 was observed when the V content was increased (V% w/w > 6.4). These fibers were very active for the propane oxidative dehydrogenation (ODH) catalytic reaction, showing very promising results since the fibrous morphology of submicrometric diameter makes these solids quite suitable for fixed-bed catalytic reactors.