The distillery vinasse is the most important liquid effluent of the ethanol production process and it is characterized by a high chemical oxygen demand (COD) and high biochemical oxygen demand (BOD); besides its acid pH and dark brown color. Phenol content in vinasse causes inhibitory effects on anaerobic digestion processes and has an adverse environmental impact. An alternative for treating vinasse from distilleries by using the electro-dissolution of iron and a heterocoagulation stage with Ca(OH)2 as a pretreatment was evaluated. Removals of 92% in phenols and 52% in chemical oxygen demand (COD) were obtained. Then, the pretreated vinasse was undergone to an anaerobic digestion process. Global removals to around 93% in biochemical oxygen demand (BOD5), 83% in COD, and over 99% in total phenols were obtained. Finally, an eco-toxicological evaluation using Daphnia pulex was carried out, and it was found that the coupling treatment increased the medium lethal concentration (LC50) to around 190%.