The catalytic activity of solid electrolytes from the family of complex bismuth vanadates Bi4V2-2x M2xO11-δ (BIMEVOX) with V5+ ions partially substituted by 3d metal cations was studied. In the transformations of isobutanol, it was found to depend on the crystal structure (α, β, γ Aurivillius phases), which changes at increased dopant ion contents (xM). The highly conductive tetragonal γ phase was most active for all BIMEVOX oxides. The activation energy of the dehydrogenation of isobutanol Ea C=O increased linearly with the charge of the M n+ ion and activation energy of conductivity of the γ phase of BIMEVOX in the series Cu2+ → Fe3+ → Zr4+. © Pleiades Publishing, Ltd. 2016.