The commercial poly(vinyl acetate) bulk was studied by nuclear magnetic resonance (NMR) at solution and solid state to understand much better the behavior of this polymer to obtain information on structure, sample molecular mobility, and heterogeneity. To analyze the behavior of this polymer, we have chosen NMR techniques, such as carbon-13 solution, magic angle spinning, cross-polarization/magic angle spinning, proton spin-relaxation time in the rotating frame parameter (T(1)rho), and dipolar dephasing experiment. Therefore, from the NMR response, poly(vinyl acetate) presents a random monomer sequence distribution along the macromolecule chains, and this provides microdomains with different mobilities.