We have developed a new experimental approach for measuring hysteresis in the adhesion between a free standing thin film and a substrate. By accurately measuring and modeling the deformations in micromachined cantilever beams that are subject to combined interfacial adhesive and applied electrostatic forces, we determine adhesion energies for advancing and receding contacts. We examined adhesion hysteresis for silane coated cantilevers and found no hysteresis at low relative humidity (RH) conditions. The dominant contribution to interfacial energy at low RH is van der Waals attraction between portions of the surfaces that are separated by nanometer asperities. In contrast, significant hysteresis was observed for surfaces that were exposed to high RH conditions. Atomic force microscopy studies of these surfaces showed spontaneous formation of silane mounds that have irreversibly transformed from initially uniform hydrophobic surface layers. Contact mechanics considerations show that the compliance of the mounds can reasonably allow microcapillaries in surrounding hydrophilic areas to bridge at high RH as the surfaces are forced into contact by an externally applied load, leading to the adhesion hysteresis.