A new method for electrochemical characterization of composite electrode materials is reported. A paste of the catalytic material in Nafion(R) is coated on a rotating ring disc electrode (RRDE) to partially simulate the working environment of a proton exchange membrane (PEM)/electrode composite as used in, for example, water electrolysis or PEM fuel cell operation. This allows direct comparison of a wide range of candidate electrocatalysts in a reproducible manner. Problems specific to these volumic electrodes are accommodated satisfactorily by rational modification of the standard expressions used in RRDE analysis. The value of the method is illustrated in studies of various cobalt complexes which show promise in dioxygen reduction; namely, cobalt tetramethoxyphenylporphyrin (CoTMPP), cobalt phthalocyanine (CoPC), and cobalt cyclam (CoCy), supported on a range of particulate carbons BP2000, Printex XE 2 and Vulcan XC-72. Typical electrochemical parameters have been measured or estimated, including half-wave potentials (E-1/2), Tafel slopes (b), 'activation currents' (I-a) and the average number of electrons transferred (n). The nature of the complex itself and the carbon support have a strong influence on electrode behaviour. Ligands with more aromatic character give better performance. Dramatic improvements in performance result from heat pretreatment, which is tentatively attributed to the formation of dimeric cobalt species via thermally-induced aggregation. In terms of the four electron reduction (to water), the best result was obtained for CoTMPP on Printex XE2 and rationalized on the basis of popular current views on the mechanism and catalyst functionality. CoPC on BP2000 is unusual in showing a strong change in n with reduction potential. Product selectivity ranges between mainly hydrogen peroxide (n = 2) and water (n = 4) with increasing overpotential.