Dyes are common pollutants in a large variety of industrial wastewaters, and the treatment of these wastes by coagulation has been extensively studied in the literature. This work is focused on the comparison of the efficiencies of the chemical and the electrochemical coagulation processes with hydrolyzing aluminum salts, and it tries to determine the similarities or differences that exist between the two coagulation processes. To do this, Eriochrome Black T solutions were used as a model of dye-polluted wastewater, and experiments of both coagulation technologies were planned to meet the same operation conditions. The pH, the aluminum concentration, the type of electrolyte, and the mode of dosing of aluminum were found to influence the process. Moreover, the speciation of aluminum was found to be the key parameter to explain the results, in terms of the mechanisms previously proposed in the literature for dissolved organic matter coagulation.