In order to improve the tribocorrosion resistance of 316 stainless steel in seawater, a protective measure of multi-interface structure CrN/CrAlN coatings was proposed. CrAlN monolayer and CrN/CrAlN multilayer coating were deposited on the surface of 316 stainless steel substrate by using multi-arc ion plating technology, respectively. The microstructure and phase composition of the coatings were characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD). The hardness and adhesion of the coatings were measured by nanoindentation and scratch tester, respectively. The continuous changes of friction coefficient and electrochemical signals of different coatings in the artificial seawater environment were recorded in real time by reciprocating friction-wear tester associated with electrochemical workstation, and the tribocorrosion characteristics of CrN/CrAlN multilayer coatings in artificial seawater environment were evaluated by analyzing the morphology of the wear scar with scanning electron microscope. The results show that, the CrN/CrAlN multilayer coating shows a compact structure with a thickness of about 4.12 μm, where the multilayer interface is clear. The mechanical properties are excellent, and the hardness is as high as 37.65 GPa. In the artificial seawater environment, friction coefficient of the coating decreases with the increase of the applied potential, and when the applied potential is 0.2 V, the lowest friction coefficient is about 0.29, while the change trend of the multilayer coating loss is the opposite. When the applied potential is –0.6 V, its lowest loss is about 0.000 86 mm3. Compared with CrAlN monolayer, the corrosion current density and the loss of CrN/CrAlN multilayer coating is significantly reduced. The CrN/CrAlN multilayer coating has a dense multi-interface structure, and has better tribocorrosion resistance in seawater environments. Its main failure mechanisms in seawater are abrasive wear, plastic deformation and corrosion wear.