The invention discloses a green synthesis method of dibenzothiazole disulfide as a rubber vulcanization accelerator, and belongs to the technical field of chemical engineering. The green synthesis method specifically comprises the following steps: completely dissolving 2-mercaptobenzothiazole in a sodium carbonate aqueous solution, then dropwise adding hydrogen peroxide, feeding carbon dioxide toadjust the pH of a system, and carrying out oxidation to generate dibenzothiazole disulfide and sodium bicarbonate. A sodium carbonate solution formed by heating the obtained sodium bicarbonate solution can be used for dissolving the raw material 2-mercaptobenzothiazole so as to realize circulation of the raw materials. The purity of the product prepared by the method can reach 99% or above. Compared with a traditional mixed acid oxidation method, the green synthesis method has the advantages that a large amount of salt-containing wastewater is reduced, and the process is environmentally friendly.