The structure and electrophysical characteristics of Bi4V2 –хFeхO11 – δ (BIFEVOX, where х = 0.3, 0.5) and its heterogeneous mixtures Bi4V2 –хFeхO11 – δ/n% FeOy and Bi4V2 –хFeхO11 – δ/m% Al2O3 are studied by varying their composition and the thermodynamic parameters of the environment. The crystallochemical parameters of individual compounds are calculated. The phase and elemental composition of samples is assessed using the XRD method and the scanning electron microscopy with energy-dispersive spectroscopic microanalysis; for individual phases, the absence of phase transitions is observed. The conductivity of materials is studied by the impedance spectroscopy. No composite effect is observed in these systems. © 2023, Pleiades Publishing, Ltd.