The invention belongs to the technical field of organic synthesis, and provides a preparation method of novel 4-phosphoryl-1, 4, 5-trisubstituted 1, 2, 3-triazole. According to the preparation method,in an organic solvent, under the action of a tetracarbonyl rhodium dichloride dimer [Rh(CO)2Cl]2 catalyst, an alkynyl phosphate compound and azide are catalyzed to prepare the 4-phosphoryl-1, 4, 5-trisubstituted 1, 2, 3-triazole. By the preparation method of the 4-phosphoryl-1, 4, 5-trisubstituted 1, 2, 3-triazole product, provided by the invention, a reaction condition is mild and the product yield is not lower than 67%. With the preparation method, the reaction condition is mild and environmentally friendly, the reaction efficiency is high, a large-scale production requirement is met better, and the prepared 4-phosphoryl-1, 4, 5-trisubstituted 1, 2, 3-triazole compound has potential physiological activity.