Different kinds of organophilic montmorillonite cotreated by cetyltrimethyl ammonium bromide (CTAB) and aminoundecanoic acid (AUA) were synthesized and applied to prepare polyurethane/montmorillonite nanocomposites via solution intercalation. The results of wide-angle X-ray diffraction (WAXD) and transmission electron microscopy showed that, for the montmorillonite modified with CTAB and CTAB/AUA (molar ratio of 1/2), an ordered intercalated nanostructure was derived, while for the montmorillonite treated with AUA, a disordered nanostructure was derived. The tensile properties of the polyurethane (PU) nanocomposites showed higher enhancement relative to PU matrix. TG showed that there is some enhancement in degradation behavior between the nanocomposites and PU matrix. DMTA results showed that nanocomposites from some organophilic montmorillonites showed a much higher storage modulus below and above glass transition temperature, while the nanocomposites from montmorillonite treated by AUA show an even lower storage modulus. The loss curves showed that the main glass transition temperature of PU was improved to some extent for the nanocomposites. The water absorption of PU and nanocomposites was also studied and the difference in reduction was thoroughly analyzed. (C) 2003 Wiley Periodicals, Inc.