Mixed oxide vanadium/antimony/titanium ammoxidation catalysts, particularly suited for the ammoxidation of alkanes and exhibiting X-ray diffraction spectra which are characteristic of a crystallographic phase of rutile TiO.sub.2, are prepared by (a) dissolving respective soluble compounds of vanadium, of antimony and of titanium in at least one saturated alcohol, (b) contacting the alcoholic solution thus obtained with water and precipitating the mixed oxide therefrom, and (c) separating and calcining the mixed oxide thus precipitated.