Slow-scan rate cyclic voltammetry (SSCV), potentiostatic intermittent titration (PITT) and electrochemical impedance spectroscopy (EIS) have been applied simultaneously to study Li ion intercalation into V2O5 films prepared by evaporative vacuum-deposition on Pt foils. Two different films, 1600 and 3600 Å thick, were used to study the influence of the film's thickness on the major electroanalytical characteristics of these intercalation electrodes. Modeling of the impedance spectrum related to the thin V2O5 film was performed using an equivalent circuit analog including the following elements: three R ∣∣ C semicircles (covering the high-frequency domain) and finite-length Warburg in sequence with the intercalation capacity (a straight line of unit slope at intermediate frequencies, and a sloping capacitive line at the very low frequencies). Sharp minima on D versus E plots, which are observed in the vicinity of the cyclic voltammetric peaks, present further evidence of very high, attractive electron–ion interactions during Li ion intercalation into the V2O5 electrode, as was already described for similar processes in graphite and some transition metal oxides: Li x CoO2, Li x NiO2, Li x Co y Ni1−y O2 and Li x Mn2O4. The diffusion length in these electrodes related to the V2O5 film's thickness.