In this paper, we investigate the inter-relationship between the conditions of the electrochemical synthesis of vanadium oxide compounds, their structural and morphological characteristics, kinetic parameters of the redox processes, and charge-discharge performance of lithium batteries with vanadium oxide cathodes. The materials studied were V2O5-y oxides and those with inserted sodium ions (Na-vanadium oxide compounds, Na-VOC) obtained electrochemically in the form of compact deposits on a metal substrate. The electrochemical synthesis of the oxides has been performed from aqueous vanadyl sulphate solutions. Optimal synthesis conditions (current density, pH, temperature, vanadyl sulphate and sodium sulphate concentrations), and subsequent optimal thermal treatment of the oxides, which provide high electrochemical activity of the cathode material and good adhesion of the oxide to the metal substrate, have been elucidated. A correlation between the structure of the vanadium oxides and Na-VOC, their morphology, impedance characteristics of the cathode, and lithium-ion solid state diffusion in the host cathode bulk has been established and discussed. A combination of analytical techniques (XRD, IR spectroscopy, TGA, BET, SEM) and electrochemical methods (cyclic voltammetry, chronopotentiometry, GITT, EIS) has been used in this study.