Superlubricity, a state of near-zero friction, offers transformative potential for minimizing energy dissipation and mechanical wear. However, realizing stable superlubricity has remained challenging due to difficulties in sustaining reliable lubricant structures. In this work, we present a feasible and straightforward strategy that integrates ionic liquids with trace amounts of low-surface-energy perfluorocarbon, yielding a robust and highly ordered monolayer film. This composite system achieves an unprecedented friction coefficient as low as 10–4, unlocking superlubricity. Furthermore, we clarify that the exceptional lubrication performance arises from precise modulation of adhesion forces at the molecular level. Our findings not only demonstrate a practical pathway to stable superlubricity but also provide fundamental insights into the underlying friction mechanisms, guiding the rational design of advanced lubricant systems with extraordinary performance and durability, which are particularly suitable for graphite-based microelectromechanical devices.