Phenol formaldehyde ortho novalac (ON) resin and 4,4′-bisisomaleimidodiphenyl methane (VS) were prepared. Bisphenol A (BPA) and ON were blended with VS in different ratios and thermally cured. The structural characterization of the synthesized and polymerized materials was done using Fourier transform infrared (FTIR) spectroscopy. The thermal curing properties of VS and its blends were investigated using differential scanning calorimetry. The temperature at which the rate of curing was maximum ( T max) was found to be varying from 210°C to 220°C. The degradation properties of the polymerized VS and its blends were studied using thermogravimetric analysis. The Friedman, corrected Flynn–Wall–Ozawa, corrected Kissinger–Akahira–Sunose, and advanced Vyazovkin methods are used to calculate the Ea-D for various reaction extents ( α). The variation of ln A with the α and thermal lifetime for these materials were predicted. The volatile products obtained during the thermal degradation of these polymers are analyzed using thermogravimetric-FTIR.