A limited number of metals may be suitable as bioanode material: noble metals, such as gold and platinum, could be the optimum choice being electrochemically inert in the operational potential window of the bioelectrochemical system. However, high costs limit their wide scale application. Even though its antimicrobial nature, copper is being considered as a promising alternative anode material, due to its high conductivity, that allows minimising the electrode material costs. Literature research indicated that high-performing electrochemically active biofilms may be grown on this metal. In the present work, gold and copper substrates have been coated by a conductive polymer (PANI), using a layer – by – layer procedure: surface grafting by reduction of 4-nitrobenzendiazonium salt was followed by reduction of nitro- to amino-groups; PANI was electrodeposited on this under-layer. The synthesized anodes were tested as working electrodes (WE) in a microbial fuel cell fed with anaerobic sludge and acetate; to assess the growth of the biofilm on the WE surface, the trend of the bioelectrocatalytic current of acetate oxidation was monitored over time. Cyclic voltammetries reveal the presence of typical redox couples related to the presence of electroactive microorganisms on the electrode surface. Preliminary data show bioelectrochemical activity on polyaniline-coated metal surfaces