Spinel type CoFe2O4 thin films have been prepared, on stainless steel supports, by thermal decomposition of aqueous solutions of mixed cobalt and iron nitrates in 1:2 molar ratio at 400 °C. The electrochemical behaviour of the CoFe2O4/1 M KOH interface was investigated by cyclic voltammetry, chronoamperometry and impedance techniques. The studies allowed finding out the redox reactions occurring at the oxide surface. The results were compared with colloidal electrodes prepared by alkaline precipitation of Fe(II) or Fe(III) hydrous oxi-hydroxides on platinum electrodes. In addition, it has been concluded that the processes are diffusion-controlled and the diffusion of the hydroxide ion, through the oxide, acts as the rate-determining step. The diffusion coefficient of OH− through the oxide film was determined using cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy techniques.