Studies show that two dimensional (2D) nanomaterial and its hybrid have a great promise in tribology for the special laminar microstructure. However, the majority of performed investigations about 2D graphitic carbon nitride (g-C3N4) nanosheets are most focused on energy storage, catalysis, adsorption, rarely tribology. In the present study, g-C3N4 supporting mono-dispersed Ag nanoparticle hybrid (g-C3N4/Ag) is prepared, and its microstructure and chemical composition are determined. More specifically, the tribological performance as the lubricating additive of poly phthalazinone ether sulfone ketone (PPESK) composite is investigated using the ball-on-disc friction tester. Moreover, the corresponding enhancement mechanism is well proposed based on the experimental analysis and theoretical simulation. Obtained results show that Ag nanoparticles with a size of about 10–20 nm are homogeneously anchored on g-C3N4 nanosheets, favoring for good compatibility between g-C3N4/Ag and PPESK. It is found that when 0.3 wt% of g-C3N4/Ag is added to PPESK, the friction coefficient and wear rate of PPESK decrease by 68.9% and 97.1%, respectively. These reductions are mainly attributed to the synergistic self-lubricating effect of Ag nanoparticles and g-C3N4 nanosheet, the formation of transfer film, as well as the limited effect of g-C3N4/Ag on the shear deformation of PPESK composite film. Furthermore, it is found that the proposed g-C3N4/Ag-PPESK composite still keeps reasonable friction-reducing and wear-resistant properties under heavy loads and high rotating speeds. The present study demonstrates that the proposed g-C3N4/Ag hybrid is an excellent lubricating additive for polymer composites.