Copolymer networks based on 4-vinylpyridine (4VPy)/crotonic acid (CrA)/divinylbenzene (DVB) and their N-oxide derivatives have been investigated by thermogravimetric analysis (TG) to evaluate their thermal stability in nitrogen atmosphere at fixed heating rate. Thermal stability was determined from TG curves to investigate the influence of 4VPy content and introduction of N-oxide groups. The TG and DTG curves of unmodified copolymers clearly show two thermodegradation stage and the same kinetic pathway. The decomposition temperatures do not depend on the 4VPy content. The copolymers modified by oxidation present lower thermostability than unmodified showing that the introduction of N-oxide groups modifies their kinetic pathways. A kinetic model Ozawa was used to determine the kinetic parameters. The apparent thermal decomposition activation energies (ΔEd) of the unmodified copolymer under nitrogen was higher than that in modified copolymer. Also, the characterizations of copolymer networks were done by Fourier transform infrared spectroscopy (FTIR). © 2007 Elsevier B.V. All rights reserved.