The electrochemical treatment of wastewaters from textile industry is a promising treatment technique for substances which are resistant to biodegradation. This paper presents the results of the electrochemical decolourisation and degradation of C.I. Reactive Orange 4 synthetic solutions (commercially known as Procion Orange MX2R). Electrolyses were carried out under galvanostatic conditions in a divided or undivided electrolytic cell. Therefore, oxidation, reduction or oxido-reduction experiences were tested. Ti/SnO(2)-Sb-Pt and stainless steel electrodes were used as anode and cathode, respectively. Degradation of the dye was followed by TOC, total nitrogen, COD and BOD(5) analyses. TOC removal after an oxidation process was higher than after oxido-reduction while COD removal after this last process was about 90%. Besides, the biodegradability of final samples after oxido-reduction process was studied and an improvement was observed. UV-Visible spectra revealed the presence of aromatic structures in solution when an electro-reduction was carried out while oxido-reduction process degraded both azo group and aromatic structures. HPLC analyses indicated the presence of a main intermediate after the reduction process with a chemical structure closely similar to 2-amine-1, 5-naphthalenedisulfonic acid. The lowest decolourisation rate corresponded to electrochemical oxidation. In these experiences a higher number of intermediates were generated as HPLC analysis demonstrated. The decolourisation process for the three electrochemical processes studied presented a pseudo-first order kinetics.