We describe in detail the advantages of a novel method of electrochemical preparation of poly ortho aminophenol (POAP), based on the ability of anionic surfactants to form micelles in aqueous media. We demonstrate that the electropolymerisation process carried out in the presence of Sodium Dodecyl Sulfate (SDS) at an oxidation potential lower than in an aqueous media yields better organized POAP films. The improved physicochemical and structural properties of POAP obtained in these conditions can be related to the electrocatalytic effect of SDS and change fractal dimension of film. With respect to Ni–POAP/G, Ni–SDS–POAP/G electrode shows a higher catalytic performance for the electrocatalytic oxidation of saccharose.