Highly adherent and homogenous polypyrrole films were electrodeposited at copper from a dihydrogen phosphate solution. The polypyrrole films were electrosynthesized in the overoxidized state by cycling the copper electrode from –0.4 to 1.8 V (SCE) in a pyrrole-containing phosphate solution. The growth of the polypyrrole films was facilitated by the initial oxidation of the copper electrode in the phosphate solution to generate a mixed copper–phosphate, copper oxide or hydroxide layer. This layer was sufficiently protective to inhibit further dissolution of the copper electrode and sufficiently conductive to enable the electropolymerization of pyrrole at the interface, and the generation of an adherent polypyrrole film. Potentiodynamic polarization measurements, Tafel analyses and open-circuit potential data revealed that the polypyrrole coating effectively protects the copper substrate from corrosion in a chloride solution. However, the corrosion protection properties were reduced with longer immersion times.