We have investigated the electrocatalytic activity of cobalt tetra-aminophthalocyanine (CoTAPc) for the one-electron oxidation of 2-mercaptoethanol (2-ME) using adsorbed monomeric CoTAPc and electropolymerized poly-CoTAPc films of different thickness on vitreous carbon electrode. Our results show that the activity of poly-CoTAPc increases slightly with the thickness of the film, while the activity of the adsorbed monomeric CoTAPc is still greatest. The trend in activities, analysed by cyclic voltammetry, is the same for the electro-oxidation of 2-ME and for the electroreduction of the corresponding disulphide. Tafel plots obtained from rotating disk measurement for adsorbed CoTAPc and poly-CoTAPc film modified electrodes show slopes close to RT/ F (ca. 70 mV) at low polarisation potentials which increase gradually with potential to values close to 2 RT/ F (120 mV). This suggests that at low polarisation the rate-determining step is a chemical step (formation of a metal complex–thiol adduct) preceded by a fast electron-transfer step involving the CoTAPc. At higher polarisations the one electron oxidation of the adduct to give the thiyl radical becomes rate controlling. Even though monomeric CoTAPc adsorbed on glassy carbon presents higher activity for the electro-oxidation of 2-ME, the high stability of the electropolymerized poly-CoTAPc makes them more attractive for applications in the activation and/or the amperometric detection of thiols.