Hydroxyterminated polybutadiene (HTPB) was reacted with 2,4-toluene diisocyanate (TDI)followed by the addition of a diamine chain extender (prepared by the condensation reaction of 4,4′-diaminodiphenylsulfone and terepthalaldehyde) to prepare an imine containing polyurethaneurea (PIUU). The prepared polyurethaneurea was caste in order to obtain polymer film. The new polyurethaneurea film showed high phenol selectivity as pervaporation membrane. About 88% phenol was obtained in condensed permeate when pervaporation was performed at 50°C with 7% aqueous phenol solution as feed and permeate side pressure was maintained at 5 mm of Hg.