Blends with various proportions of poly(vinylidene fluoride) (PVDF) and poly(methyl methacrylate) (PMMA) were prepared using melt mixing and studied by oscillatory mechanical measurements and low-field NMR spectroscopy to evaluate the influence of the processing method. The polymers and its blends were processed using a conventional low shear mixing chamber (LSM) and a high shear mixer (HSM). The behavior of all blends lies among those of the pure components, considering the two methods of characterization, and the data suggest phase separation between the two components. The hydrogen spin-lattice relaxation time of the PVDF/PMMA blends were measured and correlated with the components phases. The results are a contribution to data reported previously in the literature using different analytical methods.