Lithium-substituted sodium-vanadium bronzes of the Na2 –хLiхV12O30 (OVB) (0.6 ≤ x ≤ ≤ 1.4) were obtained from sodium and lithium formates and vanadyl formate VO(HCOO)2·H2O using soft chemistry methods. Electrochemical cycling of cells with a cathode and an anode from them, as well as with a molten lithium anode and an electrolyte based on lithium hexa-oxo zirconate was performed. It is shown, that lithium cations reversibly intercalate into bronzes of the Na2– хLiхV12O30 composition at high temperatures of 460–560°C. Using scanning electron spectroscopy (SEM) it was shown that Na2 – хLiхV12O30 OVB crystals decompose into thin plate aggregates after cycling. According to the results of energy-dispersive X-ray analysis (EDRA) it was found that there is an uneven distribution of sodium in the crystallites of the OVB phase after cycling, while maintaining the phase composition. The use of double lithium-sodium vanadium bronzes Na2 ‒ хLiхV12O30 together with lithium-conducting solid electrolytes is promising and requires further research.