The hollow MoS2 nano-particles were synthesized via hydrothermal method and were used as additives to fabricate the carbon fiber fabric/phenolic composites (CF/PF) containing WS2 micro-particles by hot-press approach. Subsequently, the tribological properties of CF/PF composites were comprehensively investigated. We found that the addition of WS2 alone can achieve significant decrease in the friction coefficient of CF/PF composites, but it decreases the wear resistance due to the peeling off of WS2 micro-particles form matrix caused by stress concentration. Nevertheless, the addition of both WS2 micro-particles and MoS2 nano-particles can achieve significant improvement in the lubricating property and wear resistance of CF/PF composites, indicating that there existed a synergetic effect among carbon fibers, WS2 micro-particles, and MoS2 nano-particles to enhance the tribological properties of CF/PF composites. The doping of additives with large size range can promote the formation of transfer film on the surface of counterpart as well as enhance the mechanical properties of matrix. Furthermore, the multi-scale additives reduced the stress concentration of matrix around the CF and hence inhibited the breakage, pull-out of CF, resulting in the improvement of the tribological properties due to the high load-carrying capacity of CF.