Surface interactions across water are central to areas from nanomedicine to colloidal stability. They are predominantly a combination of attractive but short-ranged dispersive (van der Waals) forces, and long-ranged electrostatic forces between the charged surfaces. Here we show, using a surface force balance, that electrostatic forces between two surfaces across water, one at constant charge while the other (a molecularly smooth metal surface) is at constant potential of the same sign, may revert smoothly from repulsion to attraction on progressive confinement of the aqueous intersurface gap. This remarkable effect, long predicted theoretically in the classic Gouy-Chapman (Poisson-Boltzmann) model but never previously experimentally observed, unambiguously demonstrates surface charge reversal at the metal-water surface. This experimental confirmation emphasizes the implications for interactions of dielectrics with metal surfaces in aqueous media.