The morphology structure and glass transition behavior of polybutadiene-based polyuretha-ne/polystyrene (or polymethyl methacrylate) interpenetrating polymer network (PU(HTPB)/ PSt-IPN, PU(HTPB)/PMMA-IPN) were investigated by TEM and DSC. TEM showed that the phase inversion of PU(HTPB)/PSt-IPN occurred in the concentration of 25% PU(HTPB), and the size of dispersed phase domains of the IPN formed was smaller in the concentration about 50% PU(HTPB). Increasing DVB content or proportion of NCO to OH enhanced in-terpenetration of two components. All of IPN samples exhibited special cellular structure. According to the fact that PU(HTPB) was formed first,a formation mechanism of the struc-ture was proposed.