To study the miscibility of poly(methyl acrylate)/poly(vinyl acetate) (PMA/PVAc) blend, we observed H-1 NOE difference spectra. Inter-polymer NOEs are observed, indicating that PMA and PVAc are mixed on a molecular level. The intermolecular distance between the CH3 protons of PMA and CH proton of PVAc is estimated to be 3.4 angstrom. The temperature dependence of spin-lattice relaxation time of C-13 nuclei was examined to investigate the interpolymer interaction. The motion of polymer-chain is found more hindered in blend, indicating that there exists an inter-polymer interaction in solution.