In this study, the kinetic parameters and reaction mechanism of decomposition process of oligo(4-hydroxyquinoline) synthesized by oxidative polymerization were investigated by thermogravimetric analysis (TGA) at different heating rates. TGA-derivative thermogravimetric analysis curves showed that the thermal decomposition occurred in two stages. The methods based on multiple heating rates such as Kissinger, Kim–Park, Tang, Flynn–Wall–Ozawa method (FWO), Friedman, and Kissinger–Akahira–Sunose (KAS) were used to calculate the kinetic parameters related to each decomposition stage of oligo(4-hydroxyquinoline). The activation energies obtained by Kissinger, Kim–Park, Tang, KAS, FWO, and Friedman methods were found to be 153.80, 153.89, 153.06, 152.62, 151.25, and 157.14 kJ mol−1 for the dehydration stage, 124.7, 124.71, 126.14, 123.75, 126.19, and 124.05 kJ mol−1 for the thermal decomposition stage, respectively, in the conversion range studied. The decomposition mechanism and pre-exponential factor of each decomposition stage were also determined using Coats–Redfern, van Krevelen, Horowitz–Metzger methods, and master plots. The analysis of the master plots and methods based on single heating rate showed that the mechanisms of dehydration and decomposition stage of oligo(4-hydroxyquinoline) were best described by kinetic equations of An mechanism (nucleation and growth, n = 1) and Dn mechanism (dimensional diffusion, n = 6), respectively. POLYM. ENG. SCI., 54:992–1002, 2014. © 2013 Society of Plastics Engineers