The surface modification of fibers plays a crucial role in enhancing the tribological properties of polymer composites. In this study, MoS2@basalt fiber (BF) was fabricated to evaluate the synergetic effect of MoS2@BF on the mechanical and tribological properties of polyphenylene oxide (PPO) composite. Compared to pure PPO, the bare BF can improve the mechanical property of polymer resin comparatively. By contrast, MoS2@BF can elevate the mechanical property profoundly, due to the interlocking effect of MoS2 on BF. The flexural strength and hardness of MoS2@BF/PPO were elevated by 46.7% and 22.4%, respectively, compared to PPO. And the wear rate of MoS2@BF/PPO was decreased by at least 79%, compared with pure PPO. Worn surface analysis reveals that the modification of BF surfaces with MoS2 fortifies the interface strength between BF and PPO, which can make stress effectively transmitted onto the BF rather than interface failure caused by stress concentration. Additionally, MoS2 detached from the fiber surface also can lubricate the system which refined the tribological behaviors. Analysis on cross- of steel disc worn surface uncovers that the thickness of transfer film is approximately 31.5 nm, consisting of PPO, BF, MoS2 and Iron oxide on the sliding surface, which is responsible for the excellent tribological performance.