To fundamentally understand the electrokinetic behavior of clay minerals, it is necessary to study the anisotropic surface charge properties of day surfaces. In this study, two 2:1 layer natural minerals, talc and muscovite, were chosen as representatives of magnesium and aluminum phyllosilicate minerals, respectively. The molecularly smooth basal planes of both platy minerals were obtained by cleavage along the basal planes, while suitable edge surfaces were prepared by an ultramicrotome cutting technique. Silicon nitride atomic force microscopy tip was used as a probe to study the interaction forces between the tip and clay basal/edge surfaces in aqueous solutions of various pH values. The measured interaction force profiles between the tip and clay basal/edge surfaces were fitted with the classical DLVO (Derjaguin-Landau-Verwey-Overbeek) theory, which allows direct determination of electrical surface potential of talc and muscovite surfaces. The surface potential of muscovite basal planes was found to be significantly more negative than the basal plane of talc, both being pH insensitive. In contrast, the surface potential of edge surfaces was highly pH-dependent, exhibiting a point of zero charge (PZC) at pH 7.5 and 8.1 for edges of muscovite and talc, respectively. The observed differences in surface potential of basal planes and edge surfaces for both talc and muscovite are closely related to their crystal structure and ionization characteristics. The protonation reactivity and the contribution of each surface group to the surface charging behavior are modeled using their protonation constants.