Poly(vinyl alcohol) (PVA) is a polymer of great value due to its wide spread applications. The present article describes the effect of sodium hydroxide on the flammability, thermal degradation, and tensile strength properties of PVA. The PVA/sodium hydroxide composite films at different loading levels of sodium hydroxide, i.e., 0.5, 1, 2, 3, and 4.5 wt % were prepared by solution casting technique. Dynamic thermogravimetry was used to study the thermal degradation behavior of samples at four different linear heating rates, i.e., 2.5, 5, 10, and 20 degrees C min-1 under nitrogen atmosphere. The degradation activation energy values were calculated using reliable and preferred multiple-heating rate methods. Limiting oxygen index (LOI) and UL 94 tests were carried out to check the flammability behavior of the samples. The presence of sodium hydroxide in PVA brought significant changes in the thermal and flammability performance. PVA/sodium hydroxide samples though showed lower initial decomposition temperature, but overall more thermal stability results as evidenced from the higher activation energy and char residue values. LOI and UL 94 tests indicate that sodium hydroxide greatly enhanced the flame retardancy of PVA/sodium hydroxide films. Based on the thermal and flammability level, the optimum concentration of sodium hydroxide is worked out. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013