To address the problems existing in the traditional production technique of sodium dichromate, a new green technology of producing sodium dichromate with an electrochemical synthesis method was studied. Using a self-made electrosynthesis reactor of pure titanium and stainless steel, with a multiple-unit metal oxides combination anode, a cathode of stainless steel, and a reinforcing combination cation exchange membrane with perfluorosulfonic and perfluorocarboxylic polymers, experiments were carried Out on the direct electrochemical synthesis of sodium dichromate from sodium chromate. From the experimental results and electrochemical reaction principles, it was shown that the electrochemical synthesis reaction process of sodium dichromate may be quantitatively determined from the variation of the cell voltage measured macroscopically with reaction time. Cell voltages were experimentally measured at different initial sodium chromate concentrations in the anolyte, and the dependence of the cell voltage on reaction time was discussed. The mathematical model of the variation of cell voltage with reaction time and the change rate equation of cell voltage were established, and satisfactorily formulated the change law of cell voltage in the electrochemical synthesis process of sodium dichromate.