Three different types of epoxy resins based on an unmodified epoxy (diglycidyl ether of bisphenol‐A), polyurethane (PU) modified epoxy and silicone modified polyurethane‐epoxy matrices were developed. Epoxy resin was modified with PU prepolymer and hydroxyl terminated poly (dimethyl siloxane), also referred to as ‘silicones’ using a silane crosslinking agent and tin catalyst. Aromatic polyamine adduct (A), diethylenetriamine (B) and polyamidoamine (C) were used as epoxy curatives. The formation of intercrosslinked network was confirmed using Fourier transform‐infrared (FT‐IR) spectra and viscosity data. Thermo gravimetric analysis revealed reduced thermal stability for PU (10 wt%) modified epoxy, whereas the incorporation of silicone (10 wt%) into PU modified epoxy matrix improved their thermal properties. The morphology of silicone modified PU‐epoxy was also studied by scanning electron microscopy (SEM).