For the purpose of understanding the colloidal behaviors of illite in mineral processing, probing the surface charging property of illite is of great significance. This research explored the edge and basal surfaces of illite using an atomic force microscope (AFM). The interaction forces between Si/Si3N4 probes and illite edge/basal surfaces were measured, respectively, at different pH values in 10 mM KCl solutions. Theoretical Derjaguin-Landau-Verwey-Overbeek forces were matched up with the measured forces to derive the surface potentials of the two surfaces. On the illite basal surface, an attractive force occurred at pH 3.0, while repulsive forces dominated from pH 5.0 to 10.0. On the illite edge surface, a slight attractive force was also obtained at pH 3.0. However, the interaction changed into repulsion at pH 5.0, and this repulsive force increased gradually from pH 6.0 to 10.0. Illite basal and edge surfaces were both negatively charged, but the basal surface exhibited more negative charges than the edge surface from pH 3.0 to 10.0. Increasing solution pH from 3.0 to 10.0, there was no detection of the point of zero charge (PZC) of the illite basal surface; however, the PZC of the illite edge surface should have occurred at a pH slightly lower than 3.0. This is the first time that surface potentials of illite edge and basal surfaces were attained separately by direct force measurements. These findings provide insights into the colloidal behaviors of illite in mineral processing and oil sands extraction.