The thermal degradation behaviors of poly(vinyl alcohol) (PVA) and PVA/zinc oxide (ZnO) composite are investigated using differential thermal analysis (DTA). The degradation activation energy (E_d), frequency factor (k_o) and Avrami exponent (n) as thermal kinetic parameters are calculated from the DTA results. The calculated values of E_d are 80.94 and 148.58 kJ mol^-1 for PVA and PVA/ZnO composite, respectively, indicating the enhancement of the PVA thermal stability as ZnO nanoparticles are filled in PVA matrix. The n values are evaluated from the shape analyses of degradation peaks. From estimated n values, the degradation mechanisms are determined for both the complexes under investigation.