In this article, an approach of finite element method has been introduced to predict the distribution of potential and current on electrode surfaces. In this method, the bulk of electrolyte solution and the main body of solid electrodes are modeled to be normal conductive media; while the surface of the electrode, whose current-potential (I-V) curve satisfies experimental data, is modeled to be special non-linear boundary conditions. This modeling approach for electrochemistry system is successfully verified by experimental data, and would contribute to a better understanding of the distribution of electrical potential and current at electrode surfaces in practical systems with high voltage coupling effect. (C) 2010 Elsevier Ltd. All rights reserved.