The heteronuclear oxo-cluster [VPO4](center dot+) is generated via electrospray ionization and investigated with respect to both its electronic structure as well as its gas-phase reactivity toward small hydrocarbons, thus permitting a comparison to the well-known vanadium-oxide cation [V2O4](center dot+). As described in previous studies, the latter oxide exhibits no or just minor reactivity toward small hydrocarbons, such as CH4, C2H6, C3H8, n-C4H10, and C2H4, while substitution of one vanadium by a phosphorus atom yields the reactive [VPO4](center dot+) ion; the latter brings about oxidative dehydrogenation (ODH) of saturated hydrocarbons, e.g., propane and butane as well as oxygen-atom transfer (OAT) to unsaturated hydrocarbons, e.g. ethene, at thermal conditions. Further, the gas-phase structure of [VPO4](center dot+) is determined by IR photodissociation spectroscopy and compared to that of [V2O4](center dot+). DFT calculations help to elucidate the reaction mechanism. The results underline the crucial role of phosphorus in terms of C H bond activation of hydrocarbons by mixed VPO clusters.