The mechanical, thermal, and dielectric properties of novel high performance poly(ether-ether-ketone) (PEEK)/AIN nanocomposites were discussed. The stiffness of the nanocomposites was significantly improved in the glassy state as well as rubbery state. The coefficient of thermal expansion (CTE) of the nanocomposites was found substantially lower than that of pure PEEK. The glass transition temperature and melting temperature of the nanocomposites were increased significantly. The thermal stability and dielectric constant of the nanocomposites were increased slightly with AIN content. The significant improvement in the properties of the nanocomposites was attributed to the good adhesion between the AIN nanoparticles and the polymer matrix. The fabricated nanocomposite is very promising for use in electronics packaging substrate as an alternative substrate owing to its good thermal, mechanical and dielectric properties.