A novel 3-layer organic film was fabricated on silicon wafer with a polydopamine coating (coded as PDAc) as the interlayer by a multistep self-assembly process. The formation and structure of the films were analyzed by means of ellipsometric thickness measurement, water contact angle measurement, and attenuated total reflection-Fourier transform infrared spectrometry (ATR-FTIR). Meanwhile, an atomic force microscope (AFM) characterization was performed to evaluate the adhesive and microtribological behaviors of the 3-layer film, and a ball-on-plate tribometer was used to test macrotribological performance. As results show, the as-prepared 3-layer film possessed the excellent tribological properties characterized by lower friction and higher antiwear ability, which was ascribed to the special chemical structure of the film, i.e., the strong adhesion of the film to the silicon wafer, the chemical bonding between the adjacent layers, the cross-linked structure of the PDAc interlayer, and the hydrophobicity, high flexibility, and high elasticity of the stearoyl chloride (STC) outer layer. Hopefully, the present work provides a feasible route to construct a multilayer film with excellent structural stability and tribological behavior. The titled multilayer film might find potential applications in boundary lubrication and many other areas.