Two ionic liquids, BMIM‐PF6 and BMIM‐OctSO4, are applied on Si (100) and investigated for the first time using atomic force microscopy (AFM). These liquids exhibit comparable adhesion, friction and wear characteristics relative to the perfluoropolyether lubricant Z‐TETRAOL. By configuring the AFM as a nano‐Kelvin probe, surface potential maps of the coated surfaces are obtained after wear testing.