The polycondensation kinetics of 4,4’-dihydroxydiphenyl sulfide (DHPS) with 4,4’-dichloro diphenylsulfide (DCPS) was investigated in the presence of catalyst 2A. The reaction follows second-order kinetics and the reaction rate is a bimodal, a relatively lower rate initially and a faster rate after 3h. The initially lower rate is attributed to the lower solubility of DHPS salt in organic solvent. The results show higher polymerization temperature leads to higher conversion and finial reaction extent after 7h. In the present work, catalyst 2A/DHPS molar ratio of 0.17 is considered more suitable for PPSE preparation. The activation energy of two-stage polymerization of PPSE is 104.5kJ/mol and 79.33kJ/mol, respectively. According to obtained kinetics parameters, curves of fractional conversion versus reaction time were simulated and compared with experimental curves at different temperatures.