Solid lubricants have received much attention for their use in special working conditions and limiting environments, such as high temperature, high bearing capacity, moisture, and other harsh environments. Recently, MXenes have become very attractive for their nanolaminated structure like graphite or MoS2 and weak interlayer interactions. For the first time, this work aims to fabricate various MXene composite hexafluoropropylene oxide (HFPO) oligomer acid chloride (HOAC) multilayer films and investigate their friction performance by synthesizing, exfoliating, and modifying the MXene nanosheets. Based on covalent organic framework (COF), field-emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS) results, the tribological performance and load capacity of MXene-based films modified with polydopamine (PDA) were significantly enhanced. Particularly, Si-MX/PDA-HOAC showed the best load-carrying capacity up to 600 mN and durability. It was speculated that a lubricating protection film containing FeF2 formed on the silicon/steel surfaces, showing excellent tribological properties by MXene/PDA and HOAC synergy.