Poly(vinylpyrrolidone-co-butyl acrylate) samples with different proportions of monomers were prepared as tractable and hydrophilic materials. An analysis of the intermolecular interactions between the polymer groups was carried out by FTIR. The dependence of the CO bands (lactam and pendant butyl ester) with the composition suggests a strong interaction between the lactam groups. They exert an important influence in the molecular mobility, which was studied by DSC and DRS. A single narrow glass transition temperature (T g) is observed in each random copolymer, consistent with a single phase of low compositional nanoheterogeneity. The dependence of the T g with the composition suggests significant interactions between polymer components. The dielectric spectra show γ, β, and α relaxations in increasing order of temperature, followed by conductive contributions. The apparent activation energies for secondary relaxations have similar values for all the samples. The γ-process is related to the local motions of the butyl units and the β-process is a Johari–Golstein secondary relaxation that is related to the local motions of the pyrrolidone group together with the motion of polymer backbone segments.