The processing of cross-linked polyarylene ether nitrile (PEN), which has a triazine rings structure, has been investigated under different reaction times and temperatures. In this study, the PEN films prepared by the tape-casting formed the thermally stable triazine rings by catalytic cross-linking reaction gradually, which was characterized by Fourier transform infrared spectroscopy. The chemical cross-linking reaction occurred as the CN group absorption of PEN at 2221 cm(-1) decreased and a new absorption peak, at 1682 cm(-1), was observed, and the absorption peak intensity would be progressively larger, with the extension of the processing time. After the formation of cross-linking networks, the cross-linking degree and thermal and mechanical properties of the processed films were improved substantially, compared with the untreated films. The film with added ZnCl(2) as the catalyst was more rapidly cross-linked, and its properties were better than that without catalyst at the same treatment conditions. The glass-transition temperature (T(g)) of PEN films processed at 350 degrees C for 4 h (213.65 degrees C) was higher than that of PEN films before the treatment (161 degrees C), and the tensile strength was also improved significantly. The PEN was processed at 350 degrees C for 2 h, whose initial decomposition temperature increases by about 10 degrees C, compared with that of untreated film, at one time. The rheology behavior of the cross-linked films was processed on dynamic rheometer to monitor and track the process of polymer cross-linking reaction. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 120: 1822-1828, 2011