Efficient cooperative lubrication can be achieved via the introduction of core–shell structure lubricant additives with hard core and soft shell, for obtaining the expected anti-wear performance from the structural changes in the friction process. In this study, C@Ag microspheres with a core–shell structure were prepared by the redox method with carbon spheres as the core and Ag nanoparticles as the shell. Their tribological behaviors as base oil (G1830) additive with different concentrations were investigated in detail. Compared with base oil, the addition of C@Ag particles at 0.5 wt% can reduce the coefficient of friction (COF) and wear volume (Wv) up to 15.5% and 88%, respectively. More importantly, C@Ag particles provide superior lubrication performance to single additive (like carbon sphere (CS) and Ag nanoparticle). C@Ag core–shell particles contribute to the formation of tribo-film by melt bonding of flexible Ag and carbon sphere (CS) toward excellent self-repair performance and high-efficiency lubrication. Hence, core–shell structural nanoparticles with hard-core and soft-shell hold bright future for high-performance lubrication application.