Desorption of H2O (ν = 0) following 157‐nm irradiation of amorphous solid water on a lunar impact melt breccia was measured with resonance‐enhanced multiphoton ionization. Photofragments of vibrationally excited water were detected with nonresonant ionization. The average cross section for H2O (ν = 0) removal and destruction at 0.1 Langmuir (1 L = 10−6 Torr∙s) H2O exposure was measured to be (7.1 ± 1.9) × 10−19 cm2. Cross sections were also measured at 0.3, 1, 5, and 10 L exposures. Because these cross sections increase drastically with decreasing water coverage, water is not expected to remain intact as H2O on the sunlit lunar surface. Instead, photons are likely to cause H2O to desorb or dissociate. The OH+ fragment of H2O (ν*) increased in intensity with increasing irradiation as hydroxyl groups built up on the surface and then recombined. The OH+ signal eventually began to decrease after a dose of 5 × 1018 photons cm−2. Under these conditions, the cross section for H2O (ν*) photodesorption was measured to be 6.4 × 10−20 cm2 for an initial exposure of 5 L H2O.