Our pilot research revealed that the dielectric constant of polyimide (PI) can be reduced and the modulus can be improved by assembling necklace-like interlocking complexes with crown ethers. Not only did we find that these properties of the PI complex still cannot adequately meet the demand of practical applications but also that there was a deterioration in its thermal stability. A functional octa(aminopropyl) silsesquioxane (OAPrS) with a significantly rigid Si-O-Si cage was incorporated into an 18-crown-6 (CE6)-PI (CE6-PI) complex to produce inorganic-organic OAPrS/CE6-PI nanocomposites. By exploiting the synergetic effect of OAPrS and CE6, most properties of the PI were clearly improved. In the case of 3.9 wt % OAPrS and 7.8 wt% CE6, the dielectric constant of PI was reduced by 30%, and Young's modulus and the tensile strength were increased by 106% and 23%, respectively. In addition, the thermal stability of the CE6-PI complex was modified, and its 5% weight loss temperature and glass transition temperature were increased by 31.2 and 11.2 degrees C, respectively, with the incorporation of 3.9 wff, OAPrS. The indispensable nano-reinforcing role of aggregated OAPrS crystal in the nanocomposite was carefully analysed and verified. (C) 2017 Elsevier Ltd. All rights reserved.