The electrocatalytic oxidation of a wide series of aliphatic and aromatic amines was investigated in alkaline solutions at a gold electrode modified with a Ni,Al based hydrotalcite. All the amino compounds, with the exception of pyridine, were detected by the amperometric sensor. Chronoamperometric measurements at a rotating disk allowed us to use the same modified electrode for sequential analysis of several analytes in order to investigate the factors affecting the electrochemical response. By varying the characteristics of the substrate, parameters like steric hindrance, kind of amino group, and number of oxidizable sites have been studied. The concentration ranges, where the amperometric response was linear, have been determined for the amines investigated.