The interaction of water with the clean Si(111) surface was studied with photon‐stimulated ion desorption (PSID). Results of these experiments show that water dissociates on this surface to produce Si–H and Si–OH. The Si(L) edge of the Si–H site is shifted to higher energy by 0.5 eV from the bulk. At the O(K) edge, the H+ PSID spectrum is shifted by −2.6 eV from the acid‐etched (oxidized) surface. These studies help resolve a current controversy on the water/Si(111) surface.