Substitution in rutile-type approximate to SbVO4 was made with Fe3+ and Ga3+ replacing V3+, and Nb5+ replacing Sb5+. Moreover, preparations with Ti were synthesised where Ti4+ ions substitute for both V4+ and V3+/Sb5+ pairs approximate to SbVO4-related phases containing Ti together with Fe and Ga were also prepared. The samples were characterised using X-ray diffraction, DRIFT and Raman spectroscopy. The characterisations show the formation of a cation deficient single rutile-type phase. Use of the samples in propane ammoxidation to produce acrylonitrile reveals, compared with the pure approximate to SbVO4 phase, that Fe, Ga and Ti substitution in approximate to SbVO4 results in lower activity but considerably higher selectivity to acrylonitrile at the same level of propane conversion. Niobium substitution, on the contrary, gives no improved catalytic properties. Correlations are presented between the catalytic and structural properties of the catalysts. It is demonstrated that isolation in the structure of the propane activating V-O. sites in a surrounding of nitrogen inserting Sb-sites results in improved selectivity for acrylonitrile formation. (C) 2010 Elsevier B.V. All rights reserved.