Macroscale superlubricity has attracted considerable attention as a promising strategy to minimize frictional energy dissipation and achieve near-zero wear. However, realizing macroscale superlubricity with prolonged durability remains an immense challenge, particularly on engineering steels. Current superlubricants render steel surfaces susceptible to corrosion, causing severe wear and superlubrication failure. Herein, high-entropy ceramics (HEC) with catalytic properties are innovatively introduced to prevent corrosion of engineering steels and achieve macro-superlubricity through tribo-catalytic effect. Furthermore, this catalytically induced superlubricity system exhibits an ultra-low friction coefficient of 0.0037 under contact pressure up to 1.47 GPa, an ultra-long cycle lifetime of 1.25 × 106 cycles (corresponding sliding distance up to 5 km), and an extremely low wear rate of 3.032 × 10−10 mm3·N−1·m−1 on the HEC surface. Based on the experimental analysis and theoretical simulation, the in situ formed HEC nanocrystals reduce the Gibbs free energy of hydrolysis of PA molecules into inositol and phosphoric acid molecules in the lubricant. Notably, the hydrolysis products favorably contributed to the reduction of shear force in the lubrication system, which is essential for achieving macroscale superlubricity over a long time. This study provides a new perspective for designing robust superlubricity systems by harnessing the tribocatalytic effect of high-entropy materials.