Ethylene-co-vinyl acetate and poly(vinyl acetate) blends were prepared in different proportions by melting in a HAAKE Rheomix mixer. The blends were prepared at a fixed temperature, rotation rate, and processing time. High-resolution solid-state nuclear magnetic resonance was chosen to characterize the blends with respect to structure-mobility-compatibility employing magic angle spinning with cross polarization and high-power hydrogen decoupling and the measurements of the proton spin-lattice relaxation time in the rotating frame (T(1)(H)rho). The miscibility between polymer chains was also studied by two-dimensional H-1-C-13 Shift correlation (HETCOR).