Lithium ions-doped NaV6O15 thin films have been prepared using a simple low temperature liquid phase deposition method and subsequent annealing process. X-ray diffraction (XRD), Fourier transform infrared spectrometer (FTIR), scanning elec- tron microscopy (SEM), and photoelectron spectroscopy (XPS) have been used to study the structural and physicochemical characteristics of the NaV6O15 film. The films were grown on the FTO conductive glass and used directly as an electrode of sodium ion batteries. The prepared lithium ions-doped NaV6O15 thin film electrodes showed an excellent cycling stability and discharge capacity, which may be attributed to the stability of the Li+ embedded into the gap between the V–O layers to maintain the structure and its stable β-phase structure transformed after the first cycle. The cycling stability greatly improved with increasing annealing temperature, while the discharge capacity decreased. The capacities of the film electrodes annealed at 400 °C and 450 °C maintained above 97% after 100 cycles. The lithium-doped NaV6O15 underwent a phase transition dur- ing the first charge/discharge cycle. The new transformed phase has perfect crystal structure stability undergoing insertion and deinsertion of Na+. Therefore, the lithium-doped NaV6O15 thin film possesses good cycling stability and is expected to be a promising thin film cathode for sodium-ion batteries.