Solubility of poly(vinyl alcohol) (PVA) in water prevents the preparation of various derivatives through homogeneous techniques as most of the derivatives thus formed are insoluble in aqueous medium. There are a number of solvents that can swell PVA under hot conditions but cannot dissolve PVA. In the present study, N,N-dimethyl acetamide (DMAc) has been identified as solvent in which PVA can be dissolved in the presence of an equimolar amount of lithium chloride (LiCl). H-1 nuclear magnetic resonance (H-1-NMR), C-13-NMR, infrared (IR), and X-ray diffraction (XRD) studies have been carried out to characterize the regenerated poly(vinyl alcohol) (RPVA). DMAc-LiCl is found to be a true solvent system for dissolution of PVA. An attempt has also been made to prepare poly(vinyl acetate) from this solution of PVA by a homogeneous technique.