As one of the liquid metals, Ga–In–Sn liquid metals can function as an advanced lubricant with high conductivity in a tribology system. It has already revealed advancements in several applications, such as coolants and electromechanical relays. However, Ga–In–Sn liquid metal shows poor lubrication performance on industrial metallic materials, which limits its application in engineering. In this study, the electrochemical boronising strategy was applied to improve the lubrication effect of Ga–In–Sn liquid metal on steel friction pairs. Electrochemical boronising treatment was performed to the base material AISI 52100, and a boronised layer with a thickness of around 64 μm was generated. Tribology tests were carried out on both boronised and original samples with the lubrication of Ga–In–Sn liquid metal (68.5 wt% Ga, 21.5 wt% In and 10 wt% Sn). Results show that the wear resistance of the tribo‐system reveals great improvement: The coefficient of friction decreases by 59% and the wear rate drops 85% compared to the steel/steel friction pair. EDS and XPS results show that a tribofilm consisted of Fe/Ga was in situ–generated on the wear scar of the boronised sample, which results in the synergy effect between the boronised layer and the Ga–In–Sn liquid metal. Therefore, we provided a robust strategy to enhance the lubrication performance of Ga–In–Sn liquid metal on a steel friction pair by using electrochemical boronising treatment, which could broaden the application field of Ga–In–Sn liquid metals.