Diamond-like carbon (DLC) films are valued for their high hardness and wear resistance, but their application in harsh environments is limited by high internal stress and poor corrosion resistance. Co-doping with transition metals offers a promising route to overcome these drawbacks by tailoring microstructure and enhancing multifunctional performance. However, the synergistic effects of Ni and Cr co-doping in DLC remain underexplored. In this study, Ni and Cr co-doped DLC (NiCr-DLC) films were fabricated using filtered cathodic vacuum arc deposition (FCVAD). By varying the C₂H₂ flow rate, the carbon content and microstructure evolved from columnar to fine-grained and compact structures. The optimized film (F55) achieved an ultralow surface roughness (Sa = 0.26 nm), even smoother than the Si substrate. The Ni–Cr co-doping promoted a nanocomposite structure, yielding a maximum hardness of 15.56 GPa and excellent wear resistance (wear rate: 4.45 × 10⁻⁷ mm³/N·m). Electrochemical tests revealed significantly improved corrosion resistance compared to AISI 304L stainless steel, with F55 exhibiting the highest corrosion potential, the lowest current density, and the largest impedance modulus. This work demonstrates that Ni-Cr co-doping effectively enhances the mechanical and corrosion properties of DLC films while improving surface quality, providing a viable strategy for developing robust, multifunctional protective coatings for demanding applications in aerospace, automotive, and biomedical systems.