The decolorization and TOC removal of solutions of Acid Brown 14 (AB14) diazo dye containing 50 mg L−1 of total organic carbon (TOC) have been first studied in a continuous-flow electrocoagulation (EC) reactor of 3 L capacity with Fe electrodes of ∼110 cm2 area each. Total loss of color with poor TOC removal was found in chloride, sulfate, and/or hydrogen carbonate matrices after 18 min of this treatment. The best performance was found using 5 anodes and 4 cathodes of Fe at 13.70 A and low liquid flow rate of 10 L h−1, in aerated 39.6 mM NaCl medium within a pH range of 4.0–10.0. The effluent obtained from EC was further treated by electro-Fenton (EF) using a 2.5 L pre-pilot flow plant, which was equipped with a filter-press cell comprising a Pt anode and an air-diffusion cathode for H2O2 electrogeneration. Operating with 0.10–1.0 mM Fe2+ as catalyst at pH 3.0 and 50 mA cm−2, a similar TOC removal of 68 % was found as maximal in chloride and sulfate media using the sequential EC-EF process. The EC-treated solutions were also treated by photoelectro-Fenton (PEF) employing a photoreactor with a 125 W UVA lamp. The sequential EC-PEF process yielded a much higher TOC reduction, close to 90 % and 97 % in chloride and sulfate media, respectively, due to the rapid photolysis of the final Fe(III)-carboxylate complexes. The formation of recalcitrant chloroderivatives from generated active chlorine limited the mineralization in the chloride matrix. For practical applications of this two-step technology, the high energy consumption of the UVA lamp in PEF could be reduced by using free sunlight.