The porous polyimide/hollow mesoporous silica nanoparticles (PI/HMSNs) composite films were fabricated via blending polymerization by using polystyrene (PS) microspheres as the poreâforming template. The morphologies, microstructures, thermal stability, thermal expansion coefficient (TEC), and mechanical performances of the porous PI/HMSNs films were characterized in detail. Results showed that the uniform dispersion of HMSNs benefits from the strong hydrogenâbonding interaction between the hydroxyl groups of HMSNs and poly(amic acid) chains. Both weight loss and TEC of the porous PI/HMSNs films are lower than those of the pure porous PI film. When 0.8 wt % HMSNs and 7.0 wt % PS were added into the PI matrix, the Young's modulus and tensile strength of composite film increased by about 32.4% and 68.1% compared with those of the pure porous PI film. Conclusively, the introduction of HMSNs in the porous PI matrix is an important strategy to enrich the diversity of porous structure, improve the thermal and mechanical properties of the porous PI material simultaneously. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48792.