Multilayer films based on graphene oxide (GO) and multiply-alkylated cyclopentanes (MACs) have been fabricated successfully on silicon substrate via both self-assembled and dip-coating technologies. Given the excellent mechanical properties and frictional properties of GO, the resulting multilayer films composed of GO and MACs with excellent lubricating property are expected to possess improved comprehensive tribological performances. In the current paper, the surface morphology and chemical composition of the films were analyzed using water contact angle meter, X-ray photoelectron spectroscope, and atomic force microscope. A ball-on-plate tribometer was used to evaluate the tribological performances of the films. The results showed that the new multilayer films exhibited excellent load-carrying capacity and durability. Therefore, they are hoped to find promising applications in the lubrication of microelectromechanical systems.