Although main-chain thermotropic liquid crystalline polymer (LCP) has been extensively investigated as self-reinforcing composites, tribological application is rarely reported. This paper explores tribological enhancement effect of LCP on representative matrix poly (vinylidene fluoride) (PVDF). Moreover, structures of PVDF/LCP blends are assessed in detail. Due to immiscibility, LCP in blends is uniformly dispersed in the form of particles or microfibrils, dependent on LCP content. Besides, LCP improves storage modulus of PVDF. Most importantly, tribological performance of PVDF is obviously promoted. Compared with neat PVDF, the wear rate, coefficient of friction and oscillation amplitude of blend containing 20 wt % LCP simultaneously decrease by 97.7%, 80.7% and 80.2%, respectively. In particular, frequency-enhancement phenomenon is observed. By probing worn PVDF domains with nanoindentation test and atomic force microscopy (AFM), preliminary tribological enhancement mechanism of LCP is unveiled. Overall, this finding provides a new, but promising lubrication route of polymer.