Studies of the conversion of ethane and isobutane on heteropoly oxometalates are reviewed. The mechanisms of the processes are shown to be related to the elemental composition of the anion of the catalyst and the acidic strength of the solid acids. With unsupported heteropoly oxometalates the charge balancing cations play a prominent role particularly in leading to microporous structures. Although participation of the gas phase undoubtedly occurs in the aforementioned processes, the catalyst plays an important role in the C-H bond scission. Both the conversion and selectivities in these processes are related to the strength of the terminal oxygen-anionic metal bond which itself is dependent upon the nature of the peripheral metal in the anion of the catalyst. The reductant employed in the oxidation processes appears to act primarily as a regenerator of the active oxygen species in the catalyst.