Poly(vinyl alcohol) (PVA) hybrid films containing 5 wt% pristine clay mineral were synthesized in the water solution. The various PVA hybrid films were synthesized from structurally different pristine clays: saponite (SPT), montmorillonite (MMT), hectorite (SWN), hydrophilic bentonite (PGV), and mica (Mica). The thermo-optical properties and morphologies of the PVA hybrid films were evaluated with various pristine clays. The nanostructure of the hybrid films was observed using transmission electron microscopy, which showed that the clay layers were well dispersed into the matrix polymer, although some clusters or agglomerated particles were also detected. The addition of pristine clay was more effective with regard to improving the thermal properties and gas barrier characteristics, whereas the optical transparency of the PVA hybrid films deteriorated with pristine clay.