We investigate the effects of clay proportion and nanoscale dispersion in the dielectric response of poly(vinyl alcohol)-bentonite nanocomposites. The dielectric study was performed using the thermally stimulated depolarization current technique, covering the temperature range of the secondary and high-temperature relaxation processes. Important changes in the secondary relaxations are observed at low clay contents in comparison with neat poly(vinyl alcohol) (PVA). The high-temperature processes show a complex peak, which is a combination of the glass-rubber transition and the space-charge relaxations. The analysis of these processes shows the existence of two segmental relaxations for the nanocomposites. Dielectric results were complemented by calorimetric experiments using differential scanning calorimetry. Morphologic characterization was performed by x-ray diffraction (XRD) and transmission electron microscopy (TEM). TEM and XRD results show a mixture of intercalated and exfoliated clay dispersion in a trend that promotes the exfoliated phase as the bentonite content diminishes. Dielectric and morphological results indicate the existence of polymer-clay interactions through the formation of hydrogen bounds and promoted by the exfoliated dispersion of the clay. These interactions affect not only the segmental dynamics, but also the secondary local dynamics of PVA.