Theoretical modeling and analyzing of reversible electrode reaction coupled with Langmuir adsorption is presented using cyclic reciprocal derivative chronopotentiometry (CRDCP) with symmetrical programmed current applied, in which the finite difference method was firstly used to solve the boundary value problem corresponding to the electrode processes. The algorithm described in this paper is available to solve analogous difference equations with nonlinear boundary conditions. Distinct features of dt/dE–E curves for typical models of electrode processes are obtained. If the adsorption coefficients of the electroactive species are of different orders of magnitude, the predominant peak splitting of the dt/dE–E curves can be observed, corresponding to the adsorption peaks and diffusion peaks. The sequence of the diffusion and adsorption peaks can indicate the strong adsorption of either reactant or product.