The structure of the elastomeric ethylene-propylene-diene terpolymer/atactic polypropylene (EPDM/PPA) blends were assigned by NMR using DEFT (distortionless enhancement by polarization transfer) and HETCOR (heteronuclear correlation) sequences. These methods were carried out to elucidate solid-state C-13-NMR assignments of polymeric blends.