The properties of oxide films are very important for improving the mass of ELID grinding surface. In this paper, a novel calculation model of thickness of oxide films was proposed; the theoretical calculation and simulation analysis were developed, and were compared with the corresponding experimental results. The results proved that the theoretical calculation and simulation results of the thickness of the oxide films had good agreement with the experimental results. This model could predict precisely the change of thickness of oxide film, the instinct of non-linear electrolysis was explained from a novel aspect of ability of pulsed electrolysis. This model could be used in the on-line control of electrolytic state during practical ELID grinding process.