The electrochemical synthesis of polypyrrole (PPy) on copper and brass has been successfully achieved in sodium saccharinate and pyrrole aqueous medium. The synthesized coating under several electrochemical techniques such as cyclic voltammetry, galvanostatic and potentiostatic is homogeneous and adherent. PPy has been characterized by SEM, XPS, IR and Raman spectroscopy and its quality has been confirmed. The doping level obtained from N 1s XPS signal of the oxidized PPy depends on the electrochemical technique used to produce the film. The corrosion performance of PPy/copper and PPy/brass has been evaluated in 3% NaCl and 0.1 M HCl using linear polarization and electrochemical impedance spectroscopy. The results show that PPy coating electrodeposited from sodium saccharinate exhibits significant corrosion protection properties. (c) 2006 Elsevier Ltd. All rights reserved.