An electrical equivalent circuit model of the proton exchange membrane (PEM) fuel cell system with parameters extracted through optimization is presented in this paper. The analytical formulation of the fuel cell behavior is based on a set of equations which enables to estimate his overall performance in terms of operation conditions without extensive calculations. The approach uses a set of parametrical equations and related parameters in order to characterize and predict the voltage–current characteristics of the fuel cell operation without examining in depth all physical/chemical phenomena, but including within the model different components and forms of energy actuating in the generation process. Although many models have been reported in the literature, the parameter extraction issue has been neglected. However, model parameters must be precisely identified in order to obtain accurate simulation results. The main contribution of this work is the application of Simulated Annealing (SA) as optimization method focused on the extraction of the PEM model parameters. Model validation is carried out comparing experimental and simulated results. The good agreement between the simulation and experimental results shows that the proposed model provides an accurate representation of the static and dynamic behavior for the PEM fuel cell. Therefore, the approach allows at getting the set of parameters within analytical formulation of any fuel cell. In consequence, fuel cell performance characteristics are well described as they are carried out through a methodology that simultaneously calibrates the model.