In this paper, we report on novel polyimide (PI) nanocomposites filled with binary mixtures of metal oxide (either TiO₂ or ZrO₂) nanoparticles and nanocarbon (either carbon nanofibers (CNFs) or functionalized carbon nanotubes (CNT_fs)). The structure and morphology of the materials obtained were comprehensively studied. An exhaustive investigation of their thermal and mechanical properties was performed. We revealed a synergistic effect of the nanoconstituents with regard to a number of functional characteristics of the PIs compared with single-filler nanocomposites, including thermal stability, stiffness (below and above glass transition temperature), yield point, and temperature of flowing. Moreover, the possibility of manipulating the properties of the materials by choosing a proper combination of the nanofillers was demonstrated. The results obtained can become a platform in the design of PI-based engineering materials with tailored characteristics capable of operating in extreme conditions.