In this manuscript, we report the synthesis of Li3xLa1-xVO4 (0 less than or equal to x less than or equal to 0.3) by the citrate sol-gel method. The powder and sintered samples were characterized by differential thermal analysis-thermogravimetry (DTA-TG), X-ray diffraction (XRD), transmission electron microscopy (TEM) and ac impedance techniques. The experimental results show that LaVO4 pure phase and Li3xLa1-xVO4 solid solution are formed above 650 degrees C. The diameter of the powders is about 125 nm when the molar ratio of metal ions and citric acid is 1:3. The measured magnitudes of conductivities are in the range of 10(-7)-10(-3) s cm(-1); the value of the activation energy is 31.21-34.41 kJ mol(-1) for Li3xLa1-xVO4 from 15 to 590 degrees C.