Silica–polyimide nanocomposites were prepared by hot-pressing mixtures of polyimide and highly porous silica powder. The silica powder was produced using a sol-gel process that generates pores as small as 15 Å. The effects of loading, cure, and post-cure temperature on fracture toughness were investigated. The addition of silica particles improved the fracture toughness from 0.5 to a maximum of 1.9 MPa m0.5. However, fracture toughness dropped at silica weight percentages ≥30%. The cure and post-curing temperatures have a strong influence on toughness; post-curing exposure ≥400 °C reduced toughness. Transmission electron microscopy examination of the fracture surfaces indicated that the toughness improvements may occur at the nanometer scale due to crack pinning and branching induced by the nanoporous silica particles.