Hydroxyterminated polybutadiene (HTPB) was reacted with 2,4-toluylene diisocyanate (TDI) in THF medium followed by the addition of a diamine chain extender, 4,4'-diaminodiphenyl sulfone (DADPS) to prepare polyurethaneurea (PUU). The prepared viscous polyurethaneurea solution was cast over a glass Petri dish to obtain polymer membrane. Pervaporative separation of furfural/water mixtures was performed by using prepared flat sheet hydrophobic polyurethaneurea membranes. The effect of feed composition on the membrane performance was described by the permeate flux of furfural and separation factor. The synthesized polyurethaneurea membrane was found to permeate furfural selectively with high separation factor for the organic component.