A novel modeling procedure to accurately determine the characteristic parameters of an electrochemical reaction from polarization curves is presented. Its originality is the combination of a local polynomial model of the voltammetry data with an analytical fitting, detailed in previous works. The local polynomial model is developed and validated for estimating, from one polarization curve, the noiseless current, its variance and the noise variance. These are the inputs of the analytical fitting, from which the electrochemical parameters (rate constants, charge transfer coefficients, etc.) are extracted. Therefore, the presented modeling procedure provides a quantitative description of the electrochemical reaction from one experiment. The implementation of the local polynomial model as a previous step to the analytical fitting is verified on synthetic data and proven to estimate accurately electrochemical parameters. (C) 2012 Elsevier B.V. All rights reserved.