To provide a method for producing a thiol compound containing a sulfide group and useful as a chelating agent, etc., without causing a polymerization of an alkylene sulfide in high selectivity and high yield by performing a ring-opening addition reaction of a specific alkylene sulfide with a thiol compound in a solvent such as an amide compound.

The objective thiol compound containing a sulfide group is obtained by performing a ring-opening addition reaction of an alkylene sulfide of the formula (R1 to R4 are each H, a 1-10C alkyl or a 6-15C aromatic), e.g. ethylene sulfide, with a thiol compound such as an alkanethiols in a solvent of an amide compound such as formamide, or urea-substituted compound such as 1,1,3,3-tetramethylurea, in the presence of an amine compound such as triethylamine in the method for producing the thiol compound containing the sulfide group. Further, the using amount of the amide compound or the urea- substituted compound is preferably 10-1,000 pts.wt. based 100 pts.wt. thiol compound.