In recent years, two dimensional hybrid materials have attracted immense attention in tribology field. However, kaolin shows potential value in catalysts and oil lubrication, and rarely in tribology of LC (liner composites). Herein, kaolin/Ag hybrids, in which mono-dispersed Ag nanoparticles (AgNPs) were dotted on kaolin, were prepared via in-situ reduction. The tribological behaviors of kaolin/Ag hybrids-reinforced PBO(poly(p-phenylene benzobisoxazole)/phenolic resin LC were evaluated. The results indicated that wear rate decreased but the friction coefficient slightly increased for sole kaolin filled PBO/phenolic resin LC. However, when kaolin/Ag hybrids were incorporated into PBO/phenolic resin LC, the wear rate and friction coefficient synchronously decreased. To understand the synergistic mechanism, worn surface morphology and a cross of the tribofilm via FIB-TEM analyses are provided.