We report herein on the electroanalytical behavior of Li x Na y V2O5 electrodes that were synthesized electrochemically from aqueous solutions of vanadyl and sodium sulphates, followed by thermal annealing (300°C). The electrodes were comprised of monolithic layers deposited on a stainless steel plate. A capacity above 200mAh/g could be obtained at relatively high rates (>C/3h) and prolonged cycling (hundreds of charge–discharge cycles). As evident from FTIR and XPS measurements, the electrodes develop surface films due to interactions with CO2 in the air and solution species. Electroanalytical data obtained from slow scan rate cyclic voltammetry (SSCV), potentiostatic intermittent titration (PITT), and impedance spectroscopy (EIS) are discussed.