Microcline feldspar (KAlSi3O8) is a common mineral with important roles in Earth’s ecological balance. It participates in carbon, potassium, and water cycles, contributing to CO2 sequestration, soil formation, and atmospheric ice nucleation. To understand the fundamentals of these processes, it is essential to establish microcline’s surface atomic structure and its interaction with the omnipresent water molecules. This work presents atomic-scale results on microcline’s lowest-energy surface and its interaction with water, combining ultrahigh vacuum investigations by noncontact atomic force microscopy and X-ray photoelectron spectroscopy with density functional theory calculations. An ordered array of hydroxyls bonded to silicon or aluminum readily forms on the cleaved surface at room temperature. The distinct proton affinities of these hydroxyls influence the arrangement and orientation of the first water molecules binding to the surface, holding potential implications for the subsequent condensation of water.