Friction behavior of aqueous solution at macroscale is quite different from that at nanoscale. At macroscale, tribochemistry usually occurs between lubricant and friction surfaces in the running-in process due to a high contact pressure, and most such processes can lead to friction reduction. In the present work, we reported that the hydrogen ions in aqueous solution played an important role in tribochemistry in running-in process (friction reducing process), which could result in the friction coefficient reducing from 0.4 to 0.04 between Si 3N 4 and glass surfaces at macroscale. It is found that the running-in process and low friction state are closely dependent on the concentration of hydrogen ions in the contact region between the two friction surfaces. The lubrication mechanism is attributed to tribochemical reaction occurring between hydrogen ions and surfaces in the running-in process, which forms an electrical double layer and hydration layer to lower friction force. Finally, the running-in process of H 3PO 4 (pH = 1.5) was investigated, which could realize superlubricity with an ultralow friction coefficient of about 0.004.