Catalytic compositions are provided that are effective for providing increased acrylonitrile product without a significant decrease in hydrogen cyanide and/or acetonitrile production and provide an overall increase in production of acrylonitrile, hydrogen cyanide and acetonitrile. The catalytic compositions include a complex of metal oxides and include at least about 15% m-phase plus t-phase by weight and have a weight ratio of m-phase to m-phase plus t-phase of 0.45 or greater.