The oxidation of triethylamine and tripropylamine was investigated in aqueous solution by measurement of the direct oxidation at microelectrodes or by redox catalysis at ultramicroelectrodes. An effect of pH on the homogeneous or direct oxidation was observed. In the presence of an electrogenerated oxidant such as Ru(bpy)(3)(3+), the oxidation of the amines could be achieved homogeneously. This was studied with metal complexes of different E-o [Ru(bpy)(3)(3+), Fe(bpy)(3)(3+), Mo(CN)(8)(3-), Ru(CN)(6)(3-)]. When Ru(bpy)(3)(3+) was the oxidant, the production of electrogenerated chemiluminescence (ECL) occurred. This homogeneous ECL generation was studied and the difference in ECL intensity was related to the ease of oxidation of the amine and of its intermediate radical.