Binary blends formed by two types of ethylene-co-vinyl acetate (EVA), which have different vinyl acetate contents, and poly(vinyl acetate) (PVAc) were prepared in a Haake Rheocord 9000 plastograph. A series of samples were obtained varying the PVAc amount Lip to 50%. The studies were carried out employing solid-state nuclear magnetic resonance spectroscopy (NMR) and scanning Electronic microscopy (SEM). The xenon-129 (Xe-129) and carbon-13 (C-13) NMR response together with the microscopy results showed that the systems are heterogeneous. Therefore, EVA with a higher vinyl acetate content presented some interaction between the polymer blend components.