The role of sensitivity analysis during kinetic parameter estimation is discussed in this work. An approach consisting in various steps: initialization of parameter values, nonlinear parameter estimation, and parameter sensitivity analysis, is proposed to assure that kinetic parameters are properly estimated and the convergence of the objective function to the global minimum is achieved. The method is illustrated with experimental data reported in the literature for the hydrodesulfurization of benzothiophene. The values of kinetic parameters obtained with the proposed methodology gave slightly lower values of the sum of square errors between experimental and predicted reaction rates compared with reported ones. (c) 2006 Elsevier B.V. All rights reserved.