Heterogeneous vanadium oxide compounds are produced by electrolyzing a vanadyl sulfate solution containing sodium ions. Limiting technological parameters ensuring the synthesis of electrolytic products with stable initial electrochemical characteristics are found. As sodium ions enhance adhesion of electrolytic deposits to the substrate, these can be used in the thin-layer cathodes of lithium batteries without inert additives, along with the composite electrodes containing such additives. The deposits’ electrochemical properties depend on the content of sodium ions in the electrolyte and the subsequent thermal treatment. Specific discharge capacity of such deposits may reach 320 A h kg-1 when discharged to 2.0 V at 100 ΜA cm-2.