Abstract Lithium vanadate films have been prepared on vanadium metal substrates using lithium hydroxide aqueous solutions in the autoclave by the hydrothermal-electrochemical method. The X-ray diffraction pattern of the fabricated film showed a single phase of stoichiometric crystalline orthorhombic βII-Li3VO4 without any other impurity phases. As an application of this method, we have demonstrated the direct fabrication of europium doped YVO4 films on vanadium substrate for luminescent materials using hydrothermal-electrochemical method. Those films showed sufficient intensity of luminescent property at room temperature. Therefore, this processing route may serve as an inexpensive and environmentally friendly way of the direct fabrication of the vanadate films with controlled crystal morphology and size simply by changing synthesis parameters.