The invention belongs to the organic synthesis technical field, and provides a new synthetic method of 4-(6-chloroquinoxalin-2-yloxy) phenol. In the method, alkaline aqueous solution of hydroquinone is adopted to react with 2,6-dichloroquinoxaline, and an organic solvent with a phase transfer catalyst is taken as a reaction medium to reduce side hydrolyzation reaction caused by direct contact between raw materials and alkali liquor, thus improving the stability of the whole synthetic reaction; compared with the traditional process, the synthetic method has the advantages of simple and feasible operation, higher yield and higher content, and use and recovery of the solvent greatly reduce generation of waste water, alleviate environmental pollution and lower production cost; and the corresponding excessive hydroquinone used in reaction is used with the solvent and is recovered to the most extent, thus a special hydroquinone recovery unit is not required and investment and production cost is saved; and the process is very stable in production application.