A series of graphene oxide composite lubricating films were fabricated in virtue of self-assembly technique driven by chemical bonds, which could strongly enhance interfacial interaction. The composite lubricating film Si-APS-GO-HOAF composed of GO and HFPO oligomer acid fluorides (HOAF) exhibited excellent tribological properties even immersed in 0.15 M NaCl solution for one month, attributing to strong interfacial interaction of chemical bonds and the synergistic effect of GO and HOAF. Furthermore, the outermost layer HOAF was partly adsorbed on the surface of the friction pair during the friction process and gradually formed a layer of transferred lubricating film. Surface analysis demonstrated that the formation of carbon oxide fragments and silicon oxides led to the damage of assembled layers, causing lubrication failure.