The poor adhesion between the DLC film and rubber restricts its application of seals. Introducing a suitable interlayer can bolster the adhesion of the coating or film. In this study, nitrogen-doped diamond-like carbon (N-DLC) emerged as the optimal intermediate layer between rubber and DLC. A series of N-DLC/DLC multilayer films were fabricated via DC magnetron sputtering on nitrile rubber (NBR) substrates, varying the substrate bias voltage (0 V, 100 V, 200 V). A scanning electron microscopy analysis revealed that the composite film surface was smoother than the DLC film alone. The results of Raman spectroscopy and X-ray photoelectron spectroscopy indicated a robust bond between nitrogen and carbon atoms in the composite film, with nitrogen facilitating the conversion of sp 3C-C bonds into sp 2C=C. Mechanical tests demonstrated that the N-DLC interlayer improved film adhesion and reduced the CoF of the composite film to 0.2–0.3. Specifically, the CoF of the N-DLC/DLC film prepared at 100 V was as low as 0.20, with a wear amount of 1.13 mg. Consequently, the inclusion of the N-DLC interlayer substantially enhanced the mechanical and tribological properties of DLC-coated NBR, rendering this coating highly advantageous for various applications.