We studied the interaction of water with the anatase TiO2(001) surface by means of scanning tunneling microscopy, x-ray photoelectron spectroscopy, and density functional theory calculations. Water adsorbs dissociatively on the ridges of a (1×4) reconstructed surface, resulting in a (3×4) periodic structure of hydroxyl pairs. We observed this process at 120 K, and the created hydroxyls desorb from the surface by recombination to water, which occurs below 300 K. Our calculations reveal the water dissociation mechanism and uncover a very pronounced dependence on the coverage. This strong coverage dependence is explained through water-induced reconstruction on anatase TiO2(001)-(1×4). The high intrinsic reactivity of the anatase TiO2(001) surface towards water observed here is fundamentally different from that seen on other surfaces of titania and may explain its high catalytic activity in heterogeneous catalysis and photocatalysis.