Hypothesis: Achievement of superlubricity is an effective method to reduce friction and wear, which has a prominent influence on the operational efficiency and lifetime of a device. However, some burning issues still remain to be solved for the practical applications of superlubricity, such as the poor load-bearing capacity, especially in liquid superlubricity. Therefore, exploring an effective method to enhance the superlubricity performance is essential to accelerate the application of superlubricity. Experiments: The friction properties between two different self-assembled monolayers (SAMs)?a perfluorocarbon SAM and a hydrocarbon SAM?and graphite in water were explored and compared by atomic force microscopy (AFM). Findings: Enhanced superlubricity performance due to the fluorination was observed. Specifically, we observed an approximately 85% reduction of the friction coefficient after fluorination, and superlubricity was achieved with extremely low friction coefficient of 0.0003. Moreover, 2.4-fold greater load-bearing capacity of the superlubricity was obtained after fluorination. The molecular origin of the superlubricity enhancement by fluorination was revealed by molecular dynamics (MD) simulations, indicating that the greater load-bearing capacity of the perfluorocarbon SAM was ascribed to the enhanced interaction between the water and SAM by fluorination to form a more robust layered water structure confined in the contact zone, which played a pivotal role in the superlubricity. (c) 2021 Elsevier Inc. All rights reserved.