High-performance diglycidyl ether of bisphenol-A (DGEBA) epoxy-based composite systems with improved thermal stability for advanced structural applications were developed, using bismaleimide (BMI) as toughening agent and surface-modified mullite as reinforcing agent. The nanocomposites developed in the present study are referred to as M/DGEBA-BMI. 95 % by wt. of DGEBA was toughened with 5 % by wt. of BMI and further reinforced with varying weight percentages of (0.5, 1.0 and 1.5 wt%) glycidyl-functionalized mullite to obtain M/DGEBA-BMI nanocomposites. The formation of nanocomposites was ascertained using Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy and scanning electron microscopy. The mechanical and dielectric properties of nanocomposites were investigated by analytical techniques. The thermal behaviour of nanocomposites was characterized using thermogravimetric analyzer and differential scanning calorimeter. Contact angle, surface free energy and percentage water absorption were also studied and reported. Studies suggest that the properties of M/DGEBA-BMI nanocomposites viz; mechanical, dielectric, surface energy and thermal properties improved to an appreciable extent, when compared to those of neat epoxy matrix.