This review presents the nature, fundamental structure, and various morphologies of native poly(vinyl alcohol) (PVA) matrix. It highlights recent advances in pure PVA and its composites containing various nanofillers that have potential applications in various fields. Over half a century, PVA is known as an auspicious material for diverse applications. The review focuses on the structural, mechanical, optical, and electrical properties of PVA-based nanocomposites. The study highlights a new promising area of optoelectronics for possible applications of PVA nanocomposites. The challenges and opportunities in working with various PVA nanocomposites are discussed along with some future recommendations are presented to strengthen this area of research. POLYM. ENG. SCI., 58:2119–2132, 2018. © 2018 Society of Plastics Engineers