Provided is an electrochemical synthetic method of ortho-anisidine, which includes four steps that firstly the method needs to be accomplished in an two-chamber electrolysis bath which is separated by employing a cation-exchange membrane, a copper sheet is taken as a negative electrode, a ruthenium net is taken as a positive electrode, a saturated calomel electrode is taken as a reference electrode, the negative electrode and the reference electrode are installed inside a cathode chamber of the electrolysis bath, and the positive electrode is installed inside an anode chamber of the electrolysis bath. Secondly methanol is taken as solvent, sulphuric acid is taken as supporting electrolyte, ortho-nitroanisole is taken as electrolytic reaction substrate, the solvent and solution of the supporting electrolyte are injected into the cathode chamber and the anode chamber, and the electrolytic reaction substrate is injected into the cathode chamber. Thirdly the electrolyzation is performed under the condition of normal temperature and pressure and the condition that the negative electrode is added with a certain constant voltage relative to the reference electrode, the voltage value of the constant voltage is between -0.6 to -1.0V. Fourthly after the electrolyzation is finished, the electrolyte is post-processed to prepare the product of the ortho-anisidine with the production ratio between 19.1-53.4%. The method has the advantages of simple requirement, mild reaction conditions, easy preparation of the electrodes, low price, small pollution in the process of reaction and the like, which is a greening production line.