In this work, solid-state ¹H NMR experiments were conducted to fully characterize the dynamic characteristics of a polystyrene/poly(vinyl methyl ether) blend with a mass ratio of 3 : 1 (PS/PVME 75/25). About 13% of whole PS was determined to locate in the mobile fraction of the PS/PVME 75/25 blend at room temperature. Increasing the temperature of this blend revealed three transitions. These results are expected to improve our understanding of the glass transition process in polymer systems.