In this work, the molecular mobility at the glass transition of poly(vinyl acetate) (PVAc) and poly(ethylene-co-vinyl acetate) (EVA) amorphous sample series was investigated. The temperature and pressure dependences of the intermolecular interactions were studied from time–temperature–pressure superpositions and from the relaxation time dispersion of the segmental relaxation. The difference in terms of intermolecular interactions due to the lateral group ratio of vinyl acetate (VAc) was then estimated from the activation volume and related to the cooperative behavior. The isobaric fragility and its two contributions (thermal and volumetric) were estimated through high pressure broadband dielectric spectroscopy measurements. The volumetric and thermal contributions show different behaviors as a function of the VAc ratio and as a function of the pressure. Thus, the study of the PVAc/EVA series has allowed us to emphasize that the intramolecular and intermolecular interactions induced by the dipolar pendant groups directly influence the thermal and volumetric contributions to the isobaric fragility.