The invention relates to a method for desulfurization of coal by electrochemical catalytic oxidation, although the exiting coal chemical desulfurization methods can almost remove all inorganic sulfur and part of organic sulfur in the coal, most of the methods need strong acid, strong base and strong oxidants and need to be operated under the conditions of high temperature and high pressure, the process conditions are harsh and the cost is high; furthermore, a plurality of chemical methods can cause series damages to the structure and the nature of the coal. The invention discloses the method for desulfurization of the coal by the electrochemical catalytic oxidation, which comprises the following steps: (A) adopting NaI with the concentration of 1.5mol/L as supporting electrolyte, weighing a certain amount of the electrolyte, adding into an anode chamber in an electrolysis bath, simultaneously adding the supporting electrolyte in the same volume and the same composition into a cathode chamber, and well connecting a gas collecting system; (B) adding a coal sample with the particle size of below minus 200 meshes into the anode chamber of the electrolysis bath, and controlling the concentration of coal slurry at 0.05g/ml; (C) connecting with circulating water of a water bath tank, and energizing for electrolysis; and (D) filtering electrolyte solution after energizing for 4 hours, washing the coal sample, drying, weighing and carrying out sulfur, calorific value, ash content and infrared spectrum analysis. The technology is used for the coal desulfurization.