This work mainly focuses on the development and characterization of polyimide (PI) based composite coatings filled with multi‐walled carbon nanotubes (MWCNT) on a steel substrate. The tribological properties of PI/MWCNT composite coatings at different temperatures ranging from room temperature (RT) to 200°C were investigated. Also, the influence of MWCNT and thermal & mechanical properties of PI composites coatings were measured. The addition of MWCNT could reduce the friction coefficient as well as wear volume at elevated temperatures. The PI/3MWCNT composites coatings show better wear‐resistant properties as compared to other composites. Also, the PI/MWCNT composites showed improved mechanical properties such as micro‐hardness and nanoindentation. Formation of an organic‐inorganic structure due to the inclusion of MWCNT, enhance the mechanical properties and reduce the thermo‐degradation of composites coatings. The glass transition temperature (Tg) of the PI/MWCNT composites was improved as the MWCNT content increases from 0.1 to 5 wt%.