Abstract: The effect crystal structure has on the catalytic properties of complex zirconium-containing bismuth vanadates Bi4Zr2xV2–2xO11–δ in the decomposition of isobutanol is studied. Complex oxides are obtained by means of solid-state synthesis and studied via IR spectroscopy, X-ray powder diffraction, and XPS. The catalytic activity of Bi4Zr2xV2−2xO11−δ perovskite in the dehydrogenation of isobutanol grows along with the content of zirconium(ΙV) ions and phase changes α → β → γ, with the highly conductive γ-phase being the one most active. It is found that an increase in the dehydrogenating activity of the samples is associated with a drop in the activation energy of the reaction and a change in the state of the solid solution’s current carriers. © 2020, Pleiades Publishing, Ltd.