Polyvinyl Alcohol (PVA) is a water-soluble biodegradable polymer with many industrial and biological applications. Because of its polymeric nature, reasonably high aqueous phase solubility and biodegradable properties, the use of PVA and its suitably modified derivatives as aqueous and coating phase corrosion inhibitors have acquired great recent attention. PVA and its derivatives are associated with a proper combination of hydrophilicity and hydrophobicity, essential for effective anticorrosive activity. The present review aims to describe the past and present advancements in using PVA and its derivatives as aqueous and coating phase corrosion inhibitors. Bonding of PVA with the metallic surface in anodic, basic and neutral electrolytes has also been proposed along with their orientation. They become effective by adsorbing on the metal surface. They act as mixed-type inhibitors and create a barrier to the charge transfer process. Various experimental and computational techniques are used to describe their corrosion inhibition property.