A new process technique that TiN permeation layer consisted of diffusion and deposition layer was synthesized on the surface of mild carbon steel has been firstly introduced, mainly according to plasma point discharge, hollow cathode effect and reactive vapor deposition technique. The surface appearance of this layer formed was uniform, compact and fine TiN cellular structure, a diffusion transitional region existing between the deposition layer and substrate. The surface texture was TiN deposition layer + TiN + Ti solid solution diffusion layer. From surface to inner Ti and N elements appeared graded distribution. This paper also mainly investigated the electrochemical corrosion behaviors of this multilayer. The polarization curves of specimens in 10% H2SO4 corrosive media were measured. The eroded surface morphologies were also surveyed by SEM. The results indicated that the erosion resistance of multi-permeation layer was increased many times than PVDTiN and a mild steel substrate, and almost equaled to that of compound process TiN layers.