In-situ surface-enhanced infrared absorption spectroscopy (SEIRAS) is employed to investigate the redox process of Zn 2+ /Zn on Au electrode surface in ionic liquid (IL) system containing [Bmim]BF 4 (1-butyl-3-methylimidazolium tetrafluoroborate) mixed with zinc tetrafluoroborate (Zn(BF 4 ) 2 ), within the potential range of 0.2 V~ -2.6 V. The interface structure as well as the rearrangement of the ions during the zinc electrodeposition process has been traced and explained in details. The results suggest that [Bmim] + cations integrates with anions to form high-order ions with positive charge in pure [Bmim]BF 4 . The high-order ions will be broken by Zn 2+ absorbed at the interface during zinc reduction, which leads to the reorientation of the [Bmim] + cations from a vertical configuration to a more parallel one at negative potential. Meanwhile, the [Bmim] + cations are gradually desorbed from the interface during the zinc electrodeposition process. The feature of the anions behavior is also discussed.