The anodic behaviour of copper in aqueous 0.5 M sulphuric acid containing different amounts of dissolved thiourea or formamidine disulphide was investigated at 298 K, combining data from electrochemical polarisation, chemical analysis, UV-vis spectroscopy, XPS and EDAX analysis, and structural information on copper-thiourea complexes. The main reactions depend on the applied potential and initial thiourea concentration. In the potential range -0.30 less than or equal toE less than or equal to0.075 V (versus SCE), the electro-oxidation of thiourea to formamidine disulphide, the formation of Cu(I)-thiourea soluble complexes, and Cu(I)-thiourea complex polymer-like films, are the most relevant processes. The formation of this film depends on certain critical thiourea/copper ion molar concentration ratios at the reaction interface. At low positive potentials, the former reaction is under intermediate kinetic control, with the diffusion of thiourea from the solution playing a key role. For E less than or equal to0.075 V, soluble Cu(II) ions in the solution are formed and the anodic film is gradually changed to another one consisting of copper sulphide and residual copper. The new film assists the localised electrodissolution of copper. A complex reaction pathway for copper anodisation in these media for the low and high potential range is advanced.