Dynamic operation is known as one of the factors for accelerating chemical degradation of the polymer electrolyte membrane in a polymer electrolyte membrane fuel cell (PEMFC). However, little effort has been made dealing with the quantification of the degradation process. In this investigation, cyclic current operation is carried out on a fuel cell system, and the frequency effect of cyclic operation on chemical degradation is investigated. The dynamic behavior of a fuel cell system is analyzed first with the modified Randles model, where the charge double layer is modeled by three components: a charge transfer resistance (R-ct), and two RC cells for the Warburg impedance. After calculating each parameter value through exponential curve fitting, the dynamic behaviors of the three components are simulated using MATLAB Simulink (R). Fluoride release as a function of the frequency of cyclic operation is evaluated by measuring the concentration of fluoride ion in effluent from a fuel cell exhaust. The frequency effect on chemical degradation is explained by comparing the simulated results and the fluoride release results. Two possible reasons for the accelerated degradation at cyclic operation are also suggested. (C) 2010 Elsevier B.V. All rights reserved.