Crosslinking of 2,7-bis(4-maleimidophenoxy)naphthalene (BMPN) and 4,4-bismaleimidophenylmethane (BMPM) was investigated in the presence of 4,4-diaminodiphenylmethane (DDM) at the 2/1 molar ratio of bismaleimide/DDM. Their curing behaviors were characterized by infrared spectroscopy and differential scanning calorimetry. The presence of a naphthalene group in the backbone of the bismaleimide increased the curing temperature and reduced the polymerization reactivity. The exotherm was shifted to a lower temperature as the amine addition lead to chain extension. Thermal behavior and properties of cured products were investigated by thermogravimetric analyses and dynamic mechanical analyses. Also, at this molar ratio, the properties of the BMPN/DDM showed better T-g, thermal decomposition temperature, and moisture resistance than the epoxy derived from 2,7-dihydroxynaphthalene cured with DDM system (DGEDN/DDM).