Abstract: A process for polymerization of a diene is provided. The process comprises: a) reacting the diene with hydrogen peroxide in a hydrophilic organic solvent in the presence of water to obtain a polymerization reaction mixture; b) contacting the polymerization reaction mixture with water having a temperature of from 20 to 80° C. to form a mixture having an organic phase and an aqueous phase; c) removing unreacted gaseous diene from the water mixture obtained in b); d) separating the aqueous phase comprising the hydrophilic solvent from the organic phase of the water mixture; and e) distilling volatile materials from the separated organic phase from d) to obtain the polymerization product; wherein a temperature of the reaction a) is from 50-150° C.