In this study, the multiple buffer layers process is used to enhance the optoelectronic properties of ultra thin Gallium-doped ZnO (GZO) film. Different multiple buffer layers of 0, 1, 2, 3, 4 were chosen, and the intermittent time between for each buffer layer was fixed at 10 min. The structural property of the thin film was analyzed by X-ray diffraction. The surface morphology and cross-section microstructures were observed using field emission scanning electron microscopy and high-resolution transmission electron microscopy. The resistivity and transmittance were measured by the Hall characteristic measurement system and UV–Vis–NIR spectrophotometer. The ultra thin GZO film has an optimum figure of merit of 1.47 ×10−4 Ω−1 when using the two buffer layer process. The lowest resistance is 1.1 × 10−2 Ω-cm and the average transmittance from 400 to 800 nm is about 85.25%, which promotes application of GZO on transparent conductive thin film.