Here we report on the chemical-physical characteristics and reactivity in propane ammoxidation to acrylonitrile of a new class of rutile-type, GaSbO4-based multicomponent oxides. The GaSbO4 rutile was much less active than the conventional VSbO4-based rutile systems, but showed a good selectivity to acrylonitrile. The incorporation of V in GaSbO4 allowed for an improvement in catalytic activity, but with decreased maximum selectivity to acrylonitrile. However, the further incorporation of Nb (thereby developing a Ga/V/Nb/Sb mixed oxide) led to a mixed oxide that presented an enhanced catalytic behavior, combining both high activity and high selectivity to acrylonitrile. The Nb presence also greatly improved the stability of the catalytic system, hindering the crystallization phenomena observed with rutile Ga/V/Sb/O systems. (c) 2012 Elsevier B.V. All rights reserved.