Organic–inorganic nanocomposites based on polyhedral oligomeric silsesquioxane (POSS) are regarded as a new generation of high performance materials, since they combine the two advantages of the inorganic materials (rigidity, high stability) and the organic polymers (flexibility, ductility and processibility). In this paper, a series of hybrid composites were obtained by the introduction of octa(3-amino propyl) polyhedral oligomeric silsesquioxane (NH₂-POSS) into polyamide-imide (PAI). The changes of molecular structure occurred during the synthesis are confirmed by FTIR, XRD. The impact of NH₂-POSS on the thermal, mechanical properties of the PAI and particularly tribological behaviors of PAI/PTFE lubrication coatings was investigated in detail. As expected, glass transition temperature (Tg), hydrophobic performance and mechanical properties of PAI are improved by the addition of moderate NH₂-POSS. Lower friction coefficient and wear rates can be obtained as well. What is more surprising is that the wear rate is reduced by half when the POSS content is 7wt%. It is inferred that not only the increases in the load-bearing capacity but also the reduction of surface energy can be obtained by the addition of NH₂-POSS.