The influence of electric potentials on the characteristics of modified layers with plasma nitriding of 2Cr13 stainless steel at a high temperature was investigated. Three active screens were placed on the cathodic plate. Three groups of 2Cr13 stainless steel samples were set with cathodic, anodic, and floating potentials. Samples were nitrided at 500 °C for 5 h in an ammonia atmosphere. The treated samples were analyzed using x‐ray diffraction, scanning electron microscopy with energy dispersive x‐ray spectroscopy, surface roughness tester, and atomic force microscopy. It is proved that nitriding treatments can be suitably carried out at three electric potentials, but the corresponding modified layers take on different microstructure, morphology, and hardness behaviors. It found that the three nitrided samples are mainly composed of the ϵ−Fe2‐3N and γ’−Fe4N phases. The order of thicknesses of the nitrided layers is: floating < anodic < cathodic potential. The results also demonstrated that electric potentials play essential roles in the corrosion resistance and tribological properties in plasma nitriding treatment. Because there is no visible precipitation of chromium nitride in the modified layer, the corrosion resistance of the floating nitrided sample is better than that of the other two samples.