The fundamental mechanism of the improved damping properties of poly(vinyl acetate) (PVAc), contributed by the introduction of hindered phenols, was systematically elucidated by two-dimensional infrared (2D IR) spectroscopy, dynamic mechanical analysis (DMA), differential scanning calorimeter (DSC), X-ray diffraction (XRD) and molecular dynamics (MD) simulation. The 2D IR results revealed the evolution of hydrogen bonds (H-bonds) from intermolecular H-bonds to H-bond networks of PVAc/hindered phenols. Note that subsequent DMA results revealed that the damping properties of PVAc exhibited two different degrees of improvement due to the addition of hindered phenol. Moreover, DSC results showed that all hybrids were miscible, as concentration fluctuations changed irregularly. In accordance with the XRD observation of only amorphous hindered phenols existing in the PVAc matrix, further MD simulation, based on an amorphous cell, characterized the number of H-bonds, the binding energy and the fractional free volume (FFV) of the hybrids. It was observed that the variation tendency of the simulation data was in accordance with the experimental results. Therefore, the damping mechanism of PVAc/hindered phenol hybrids was proposed through a detailed analysis on the synergistic effect of the number of intermolecular H-bonds and the binding energy between PVAc and the hindered phenol, as well as the FFV or dynamic heterogeneity.