Solid state reactions of Bi2O3 with MexOy, oxides were studied by means of the Bi2O3 / MexOy coupled anneals in model cells where MexOy were the oxides of II-VI groups and 3-d metals. The reactions were performed both in spontaneous and external electrical field applied modes. The following main features are revealed and discussed: the dependence of Bi2O3 diffusion ability, mass- and charge-transfer routes upon the oxidation degree of metal in partner oxide, formation of O2- solid electrolyte phases at the Bi2O3 / MexOy interface, the drastic influence of the reaction rate and product composition upon the external voltage and polarity for reactions with 3-d metals and Cr oxides connected with easy change of Me oxidation degree at the support/product interface.