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The phase structures of a series of ethylene-dimethylaminoethyl methacrylate (EDAM) copolymer samples were investigated by solid-state high-resolution ¹³C n.m.r. spectroscopy. It is found that at least the α and β methylene units relative to the tertiary carbon of dimethylaminoethyl methacrylate (DAM) along the molecular chain as well as DAM comonomer units are located outside the crytalline region. The ¹³C CP-MAS spectra also reveal that with increasing DAM content, the ratio of monoclinic to orthorhombic crystals increase as well as the ratio of interfacial to crystalline regions.