Synthetic solutions containing up to 2000 ppm of gallotannic acid and real wastewater from vegetal tanning processes with values of chemical oxygen demand (COD) exceeding 100 000 ppm were decontaminated by electrolysis using a sacrificial iron anode coupled to either a titanium-platinised or an O-2-diffusion cathode. Experiments were performed in the presence of oxidants and oxidation promoters such as air, oxygen and hydrogen peroxide, the latter being directly added to the solution or electrogenerated by the O-2-diffusion cathode. COD and UV-visible absorbance evolution showed that tannins are removed from electrolysed solutions down to relatively low values, permitting more than 94% elimination. Partial oxidation of the mother compound generates short-chain by-products (mostly carboxylic acids) responsible for the remaining low COD values. Contaminants (tannins and non-tannins) contained in industrial wastewater were removed by combining electroprecipitation with a Fenton-assisted process; a final oxidation step, carried out on a boron-doped diamond electrode, was performed in order to decrease the COD to very low final values.