An atomic force microscope, employing the colloidal probe technique, was used to study the interactions between six different combinations of silane-functionalized silica surfaces in NaCl and CaCl2 solutions. The surfaces consisted of monolayers of the apolar trimethoxy(octyl)silane, the positively charged (3-aminopropyl)trimethoxysilane, and the negatively charged (3-mercaptopropyl)trimethoxysilane. The interactions between the three symmetric systems, as well as between the three asymmetric combinations of surfaces, were measured and compared to calculated electrical double-layer forces. The results demonstrated that the long-range interactions between the surfaces in all cases were dominated by double-layer forces, while short-range interactions, including adhesion, were dominated by ion bridging forces in the cases where both interaction surfaces favored adsorption of calcium ions. The study thus also demonstrates how surface force studies in mono- and divalent salt solutions can be used as an analytical tool for probing specific functional groups on heterogeneous surfaces.