A novel preparation method of BIMEVOX materials involving the decomposition of a well dispersed cation gel is described, allowing a simple, rapid manufacturing of bismuth-vanadium oxide based membranes. A detailed investigation of the required oxidative decomposition and the sintering procedure was performed, indicating the conditions for a complete removal of carbon containing compounds and the formation of dense samples. Differently doped BIMEVOX materials were prepared and investigations on the interaction of gas-phase oxygen with the membrane material were carried out. For the first time, the oxygen transfer from the gas phase to the bulk was studied directly by the highly time resolved TAP transient technique.