Cure reactions of a bismaleimide (4,4-bismaleimidodiphenylmethane, BMI) associated with a liquid aromatic dicyanate ester (1,1'-bis(4-cyanatophenyl)ethane, BEDCy) and with a powder type aromatic dicyanate ester (bisphenol A dicyanate, BADCy) were investigated by in situ FTIR and DSC dynamic scanning. In non-catalyzed blend systems, co-reactions between dicyanate ester and bismaleimide always occur, and hence the formation of pyrimidine and/or pyridine structures take place. Pyrimidine structures always predominate. Probable reaction paths were also proposed for various formulations of hybrid blends. In addition, N-phenylmaleimide (MI) and p-phenyl-phenylcyanate (S-Cy) were utilized as model compounds and mixed via a melting method and a solution method to explore the corresponding cure reactions by means of FTIR, DSC and NMR. C-13 NMR spectra of the model compounds demonstrated the formation of linkages of sym-triazine rings, pyrimidine structures, pyridine structures and dioxazine structures. The reaction mechanism or linkage structures produced in the model compound system studied may be somewhat different from those of the real system due to a diffusion effect in real systems or to the different activation energy in both systems. (C) 2004 Elsevier Ltd. All rights reserved.