Abstract: A polyarylene sulfide having a high molecular weight is produced at low cost and without causing any pollution problems through a polymerization reaction between a dihalogenated aromatic compound and an alkali metal sulfide in an aprotic polar solvent by adding from about 0.05 to about 5 moles of calcium chloride per mole of the dihalogenated aromatic compound after the conversion of the dihalogenated aromatic compound has reached about 60 to about 98 mol % and allowing the reaction to proceed. Such a polyarylene sulfide is very useful for utilization in extrusion of films, fibers, etc.