A series of electrochemical tests combined with the techniques of scanning electron microscopy (SEM), electron backscatter diffraction (EBSD) and X-ray photoelectron spectroscopy (XPS) were used to study the effect of nitrogen content on the composition, structure and protectiveness of passive films, which were formed on the surfaces of high-nitrogen austenitic stainless steels (HNSS) in 0.5 mol/L NaCl solution. The results showed that the HNSS with higher nitrogen content had a larger proportion of low-angle grain boundaries, and it also had a lower corrosion current density in 0.5 mol/L NaCl solution and thus a lower corrosion rate. The existence of a larger proportion of stable oxides (e.g., Cr2O3) in the passive films facilitates the passivation/repassivation process and contributes to the high corrosion resistance of HNSS.