A new method for improving the processability and thermal stability of commercially available poly(vinyl alcohol) is presented involving the reaction of the hydroxyl group on the polymer backbone with long-chain aliphatic, cycloaliphatic, and aromatic epoxides. The reaction was performed in the molten phase using a laboratory-scale thermostated reactor. As expected, the extent of the reaction varied with the chemical structure of the epoxide, the properties of polymers obtained being dependent on the amount of the incorporated side group. Specifically, the reactivity of long aliphatic chain epoxides was low and the polymers obtained exhibited a small decrease in the melting points, being directly proportional to the length of the aliphatic chain. They displayed, however, improvement in thermal stability compared to the parent polymer. Cyclohexene oxide was appreciably more reactive and it exhibited a larger melting point reduction and satisfactory thermal stability. Polymers functionalized with aromatic rings and prepared under the same conditions were mostly amorphous, not showing melting point transition or improvement in their thermal stability. Finally, the reactions with aliphatic epoxides were catalyzed with phosphoric acid and the modified polymer exhibited a large decrease in the melting point but not a concomitant improvement in thermal stability.