Functionalized polypyrrole film were prepared by incorporation of (Fe(CN)(6))(4-) as doping anion, during the electropolymerization of pyrrole onto a carbon paste electrode (CPE) in aqueous solution by using potentiostatic method. The electrochemical behavior of the (Fe(CN)(6))(3-)/(Fe(CN)(6))(4-) redox couple in polypyrrole was studied by cyclic voltammetry and double step potential chronoamperometry methods. In this study, an obvious surface redox reaction was observed and dependence of this reaction on the solution pH was illustrated. The electrocatalytic ability of polypyrrole/ferrocyanide films modified carbon paste electrode (Ppy/FCNMCPEs) was demonstrated by oxidation of ascorbic acid. It has been found that under optimum condition (pH 7.00), the oxidation of ascorbic acid at the surface of such electrode occurs at a potential about 540 mV less positive than unmodified carbon paste electrode. The kinetic parameters such as electron transfer coefficient, alpha and catalytic reaction rate constant, k(h)'(,) were also determined by using various electrochemical approaches.The catalytic oxidation peak current showed a linear dependent on the ascorbic acid concentration and a linear calibration curve was obtained in the range of 4.5 x 10(-4) to 9.62 x 10(-3) M of ascorbic acid with a correlation coefficient of 0.9999. The detection limit (2sigma) was determined as 5.82 x 10(-5) M. (C) 2003 Published by Elsevier Ltd.