The bis(hydroxyphenyl) sulfides mixture prepared according to the inventive method is advantageous in respect of the increased proportion of 4-mercaptophenol relative to less useful 2-mercaptophenol in the product obtained by the reductive decomposition of the mixture. The inventive method is characterized by performing the reaction of phenol and sulfur chloride in a specific solvent which is an ethylene glycol monoalkyl ether compound such as ethylene glycol monomethyl ether, triethylene glycol monoethyl ether and the like.