An electrochemical process for the production of a hydroxide solution and a sulfate by the electrolysis of a waste aqueous mixture of oxidizable sulfur impurities in the anode compartment of at least one electrolytic cell while producing a hydroxide solution in the cathode compartment of the cell. The process is particularly applicable to the treatment of spent caustic solutions obtained by scrubbing a hydrocarbon process stream contaminated with oxidizable sulfur impurities. The electrolytic cell used in the electrolysis process of the invention can use either a porous membrane or a cationic permselective membrane to separate the anode and cathode compartments of the electrolysis cell. The electrolysis cell can be monopolar or bipolar and when bipolar, the bipolar electrodes if dissimilar, or the respective anode and cathode current collectors if dissimilar, which are attached thereto, are electrically connected by bonding with a conductive polymer or are joined by welding with or without an intermediate metal layer therebetween. Control of pH in the anolyte compartment of the electrolytic cell can be achieved by passing a selected amount of catholyte to the anolyte compartment. Pre-treatment with oxygen produced in the anolyte compartment of the cell avoids release of gaseous products from the anolyte compartment and increases process efficiency. Where the process is conducted in multiple electrolytic cells, such cells are hydraulically connected in a cascading series.