Thin films of controlled thickness of Co/Al layered double hydroxide with different Co and Al percentages have been electrosynthesized by the cathodic reduction of a 0.03 M Co and Al nitrate solution. The electrochemical behaviour of the films deposited on Pt or ITO electrodes has been deeply studied in 0.1 M NaOH solution. Our findings demonstrate that as soon as a potential is applied in the anodic direction, the films undergo an irreversible change of phase. (c) 2008 Elsevier Ltd. All rights reserved.