Phase structures of nylon-11/polyepichlorohydrin (Ny-11/PECH) blends are studied by nuclear magnetic resonance, differential scanning calorimetry and transmission electron microscopy techniques. In the solid state, although the domain size of these mechanical blends is 1-2 mu m, blending does change the motional states/phase structures of the two components. The motional freedom of PECH chains decreases as the composition of Ny-11 increases in the blends. The amorphous phase of Ny-11 changes less after blending, but increasing PECH in the blends causes the crystalline phase of Ny-11 to be disordered and the crystallinity of Ny-11 component to decrease. When the blend is PECH-rich, the crystalline phase of Ny-11 component disappears. The two-dimensional nuclear Overhauser effect result indicates that there are intermolecular interactions between Ny-11 and linear PECH chains, and the system is miscible in dimethylsulfoxide solution.