CrN and diamond-like carbon (DLC) coatings are deposited on the surface of 431 stainless steel by the direct current magnetron sputtering technique. The surface morphology, micro-structure, hardness, friction, and wear properties of CrN, CrN/DLC and multi-layer composite DLC coatings are investigated by scanning electron microscopy, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, nanoindentation tester, scratch tester, and friction and wear tester. The results show that the surface of the single CrN coating is very rough for the columnar crystal structure with preferred orientation. When it serves as inner transition layers to form the composite DLC coatings, the surface gets much smoother, with reduced defects. The friction and wear results indicate that the composite DLC coatings exhibit lower coefficients of friction, and better wear and corrosion resistance in dry friction, deionized water, and seawater. In the dry wear and friction process, the single CrN coating is easily worn out, and severe friction oxidation and furrow wear both appear with a friction coefficient of 0.48. But the friction coefficient of a CrN coating in seawater is reduced to 0.16, and friction oxidation and wear loss are further reduced with water lubrication. The CrN/DLC coating has excellent tribological performance in three test concoctions and has the lowest friction coefficient of 0.08 in seawater, which is related to the higher sp 3 bond content, density (1.907 g/cm 3) and high degree of amorphization, contributing to high hardness and a self-lubrication effect. However, due to the limited thickness of CrN/DLC (1.14 µm), it easily peels off and fails during friction and wear in different testing conditions. In multi-layer composite DLC coatings, there are more sp 2 bonds with decreased amorphization, high enough thickness (4.02 µm), and increased bonding strength for the formation of different carbides and nitrides of chromium as transition layers, which gives rise to the further decreased average friction coefficient and the lowest wear loss. Therefore, the CrN coating alone has good wear resistance, and, as with the inner transition layer with a DLC coating, it can effectively improve the overall thickness and the bonding strength of the multi-layer films by optimizing the chemical compounds of DLC coatings. These results provide experimental support and reference for the design and selection of surface coatings for 431 stainless steels in different working conditions.