Improving the tribological performance of carbon fabric (CF)/polymer composites is vitally significant for developing high-performance lubricating materials. We propose the combination of interfacial modification and use of a lubricant additive to enhance the antifriction and anti-wear properties of CF/phenolic (PF) composites. And the tribological properties of CF/PF composites were characterized using ball-on-disc friction and wear tester. First, ZnO nanorods were densely and uniformly grown on the carbon fiber surface using POSS as a bridge molecule to make fiber with a rough micro-nano microstructure and active functional groups; this was conducive to enhancing the interlaminar shear strength (ILSS) and wear resistance of CF/PF. Then, graphite (Gr) was further introduced as a lubrication additive into the modified CF-POSS-ZnO/PF to increase the friction-reducing capacity. The corresponding modified composite with 5 wt% Gr demonstrated outstanding tribological performance. The coefficient of friction and wear rate decreased by 55.37% and 93.36%, respectively, compared to those of CF/PF. Moreover, it still retained outstanding friction and wear properties in the sliding process with high loads and speeds. The synergistic mechanism of interfacial modification and lubricant additive on the tribological performance of CF/PF are discussed systematically on the basis of the analysis of the ILSS, fracture surface microstructures, and worn surfaces of the composites. This work might shed new light on the design and development of high antifriction and anti-wear CF/polymer composites.