The admixture of graphene oxide (GO) sheets and chloroacetic acid were ultrasonic treated. As a result, epoxy and hydroxyl groups which existed onto GO sheets were transformed into carboxyl groups. Then, the carboxyl-GO sheets were assembled on silicon substrate by taking use of 3-aminopropyltriethoxysilane (APS) as an intermediate coupling agent (marked as APS-GO). Furthermore, La elements were deposited on the APS-GO by means of chemisorption to form multilayer film (APS-GO-La). Chemical compositions, surface morphologies, and microstructures were investigated by using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and water contact angle (WCA). Experimental results suggested that carboxyl-GO sheets distributed homogeneously on Si substrate. Results also indicated that lanthanum elements can react with the-COOH functional groups of GO film and be adsorbed on the APS-GO film surface. The prepared APS-GO-La multilayer film showed low surface free energy, which has potential applications in nano/micro electro-mechanical systems (N/MEMS).