Thin films of lithium ion conductive ceramic Li4+xAlxSi1-xO4 were fabricated on Au substrate using sol-gel process. The sol of Li-Al-Si-O was spread on Au substrate using a spin coater, and it was gelated at room temperature. The gel was calcinated at 400 °C and heat-treated at high temperatures between 500 °C and 800 °C in air. The addition of poly(vinylpyrrolidone) (PVP) was effective in stabilizing the sol. Furthermore, the morphology of the obtained thin film was changed by the PVP additive. Li4+xAlxSi1-xO4 thin film prepared at 800 °C exhibited a Li+ ion conductivity of 10-8 S cm-1 at room temperature.