The work aims to improve the tribological properties of glycerin as a lubricant. A novel halogen-free functionalized imidazole ionic liquid (M-16-DOSS) was prepared as a lubricant additive for glycerin. The structure of M-16-DOSS was characterized by nuclear magnetic resonance and high-resolution quadrupole time-of-flight mass spectrometry; the thermal stability of the glycerin lubrication system was tested by a synchronous thermal analyzer; the friction and wear performance of the glycerin lubcaition system were evaluated by the SRV-IV micro-friction and wear tester and the wear volume and wear spot morphology were characterized by three-dimensional profilometer; and the surface elements and chemical morphology of wear spots were analyzed by EDS and XPS. The synthesized functionalized imidazole salt ionic liquid had the correct structure and qualified purity. M-16-DOSS had good compatibility with glycerin and could improve the thermal stability of glycerin. As a lubricant additive of glycerin, M-16-DOSS could significantly improve the tribological properties of glycerin. When the amount of M-16-DOSS was 1.5wt%, the friction coefficient decreased to 0.1 and the wear volume decreased by 80%. A tribochemical reaction occurs during the friction process. A chemical reaction protective film is formed with iron and oxygen through the synergistic effect of sulfur and nitrogen, which effectively buffers the direct contact and collision between friction pairs, and improves the anti-friction andante-wear performance of glycerin. This new type of functionalized imidazole ionic liquid has excellent properties and provides new ideas and options for the development of glycerin lubricant additives.