The potential sensor materials of scroll-like dodecylamine-templated vanadium oxide VOx nanotubes doped with Co2+ or Fe3+ have been prepared using a sol-gel technique followed by the hydrothermal treatment. The resultant samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning and transmission electron microscopies, thermal and elemental analysis. The gas sensing properties of the metal cations doped VOx nanotubes have been tested in the wide range of working temperatures and targets’ concentrations towards ammonia, ethanol, methanol, toluene and acetone. The highest sensor activity was revealed for ethanol. Stability and electronic properties of pristine and metal doped VOx layers as well as their ad-complexes with O2 as intermediates during the working process of a sensor were studied by DFT calculations. The study suggests two different mechanisms of cations' action on sensing properties of a VOx compound. In absence of steric obstacles, Co2+ doing is predicted to be the most efficient dopants for beneficial activation of VOx sensing properties.