Poly(vinyl alcohol) (PVA) has been considered as an important commercial synthetic thermoplastic polymer. PVA is a low cost, reasonably processable, optically transmitting, heat stable, and mechanically robust plastic. PVA-based nanomaterials usually comprise of the nanocomposites (PVA/graphene, PVA/carbon nanotube, PVA/nanodiamond, PVA/metal nanoparticle) and nanofibers. The structural, optical, mechanical, and electrical properties of the PVA-based nanomaterials have been enhanced with nanofiller addition or nanostructuring. This review offers fundamentals and advanced aspects of poly(vinyl alcohol) and the derived nanomaterials. It highlights recent advances in PVA nanocomposites and nanofibers for potential applications. The PVA-based nanomaterials have been successfully employed in fuel cells, sensors, batteries, membranes, electronics, and drug delivery relevances. The challenges and opportunities to strengthen the research fields of PVA-based nanomaterials have also been presented.