A series of novel crosslinked PU composites were synthesized using polytetramethylene (PTMG), toluene diisocyanate (TDI), 3,5-dimethylthiotoluenediamine (DAMTDA, E-300) as raw materials, and glycine-calcium bromide (GCB) semi-organic crystal and GCB-crystal mixed SiO 2 or 13X-zeolite respectively as modifier by a prepolymer method. The macroscopic property and microstructure were characterized by mechanical tests, atomic force microscopy (AFM) analysis and dynamic mechanical analysis (DMA). The results showed that effects of different composite particles on the microphase separation of novel crosslinked PU composites were different. The extent of the microphase separation of PU composites was showed by AFM analysis visually. And the results of DMA not only gave the information about energy storage modulus, energy dissipation modulus and the microphase separation of PU composites, but also reflected the interaction between the macromolecular chains and nanoparticles preferably.