A series of polyurethane (PU) films made from toluene diisocyanate (TDI), 1,4-butanediol (BDO), and hydroxyl-terminated polybutadiene (HTPB), hydroxyl terminated polybutadiene/styrene (HTBS), or hydroxyl terminated polybutadiene/acrylonitrile (HTBN) was synthesized by solution polymerization. The absorption of benzene vapor was found mainly in the soft phase. The equilibrium adsorption (M-infinity) was reduced with increasing hard segment content for all the PUs. The values of M-infinity were in the sequence of HTBN-PUs > HTBS-PUs > HTPB-PUs, which could be explained by the different interaction parameters between soft segments and benzene. The HTBN-PU film showed the lowest degree of phase segregation and had more hard segments intermixed in the soft phase, restricting the movement of soft segments, and therefore resulted to non-Fickian behavior, while the HTPB-PU is antithetical. FTIR and atomic force microscopy were utilized to identify the hydrogen bonding behavior and morphology change of the PU films before and after the absorption of benzene vapor. The tensile strength of the HTBN-PUs showed a greater decrease than that of HTBS-PUs and HTPB-PUs after absorbing benzene vapor. (C) 2004 Wiley Periodicals, Inc.