Some 'conductive' hydrotalcites containing nickel as divalent cation and Cl-, SO42- or CO32- as interlayer anion, have been synthesised and membranised with different types of polymeric matrices to modify glassy carbon electrodes. The mechanism responsible of the conductive properties has been deeply investigated by voltarnmetric techniques using both a stationary and a rotating disk electrode, demonstrating that the interlayer anion does not affect significantly the electrochemical behaviour of the material. The electrocatalytic properties have been also studied pointing out the key role of the steric hindrance of the oxidisable substrate. In particular, mono- and polyhydric compounds have been taken into account. As to the electrocatalytic efficiency, the nature of the interlayer anion and, hence, the dimension of the interlayer spacing, is important in determining the sensitivity of the measurement since it can affect the analyte diffusion inside the hydrotalcite structure.