Lithium transport through vanadium pentoxide xerogel film electrode has been investigated in a 1M solution of LiClO4 in propylene carbonate by employing potentiostatic current transient technique and ac-impedance spectroscopy. From the comparison of the initial current experimentally measured with those initial currents theoretically calculated from the Ohm’s law and the Cottrell equation, it was confirmed that the cell-impedance-controlled constraint at the electrode surface is changed to the real potentiostatic boundary condition (diffusion-controlled constraint) when the potential step exceeds a critical value over the whole range of the lithium content. It was also found that the slope of the logarithmic current transient obtained at the lithium contents above 0.4 positively deviates in absolute value from 0.5 even under the real potentiostatic boundary condition, but the phase angle of the diffusion impedance under the semi-infinite diffusion condition negatively deviates in absolute value from 45° with increasing lithium content. With the aid of the X-ray diffractometry, the anomalous behaviours of the current transient and the diffusion impedance were discussed in terms of lithium transport through the interlayers with widely distributed spacings across the quasi-ordered xerogel film electrode. Furthermore, the current transient theoretically determined by employing the concept of interlayer spacing distribution coincided fairly well in form with that current transient experimentally measured.