Quasielastic neutron scattering, x-ray diffraction measurements, and fully atomistic molecular dynamics simulations have been performed on poly(vinylpyrrolidone) homopolymer above its glass transition temperature. A “prepeak” appears in the x-ray diffraction pattern that shows the typical features of a first amorphous halo. From an effective description of the experimentally accessed incoherent scattering function of hydrogens in terms of a stretched exponential function, we observe enhanced stretching and a momentum-transfer dependence of the characteristic time different from that usually reported for more simple polymers (main-chain polymers or polymers with small side groups). The comparison with both kinds of experimental results has validated the simulations. The analysis of the simulated structure factor points to a nanosegregation of side groups (SG) and main-chains (MC). The detailed insight provided by the simulations on the atomic trajectories reveals a partial and spatially localized decoupling of MC and SG dynamics at length scales between the average SG–SG distance and the characteristic length of the backbone interchain correlations. Anomalous behavior in correlators calculated for the SG subsystem are found, like e.g., logarithmiclike decays of the density–density correlation function. They might be a consequence of the existing large dynamic asymmetry between SG and MC subsystems. Our results suggest that, as the SGs are spatially extended and chemically different from the backbone, they form transient nanosegregated domains. The dynamics of these domains show similar behavior to that found in other systems displaying large dynamic asymmetry.