Cations can achieve excellent hydration lubrication at smooth interfaces under both microscale and macroscale conditions due to the boundary layer composed of hydration shells surrounding charges, but what about anions? Commonly used friction pairs are negatively charged at the solid/solution interface. Achieving anionic adsorption through constructing positively charged surfaces is a prerequisite for studying the hydration lubrication of anions. Here we report the hydration layer composed of anions adsorbed on the positively charged polymer/sapphire interface at acidic electrolyte solutions with pH below the isoelectric point, which contributes to the hydration lubrication of anions. Strongly hydrated anions (for the case of SO42–) exhibit stable superlubricity comparable to cations, with strikingly low boundary friction coefficient of 0.003–0.007 under contact pressures above 15 MPa without a running-in period. The hydration lubrication performance of anions is determined by both the ionic hydration strength and ion adsorption density based on the surface potential and tribological experiments. The results shed light on the role of anions in superlubricity and hydration lubrication, which may be relevant for understanding the lubrication mechanism and improving lubrication performance in acidic environments, for example, in acid pumps, sealing rings of compressors for handling acidic media, and processing devices of nuclear waste.