We report high resolution photoelectron imaging spectra of Cu- and Cu-(H2O)(n) (n = 1,2) complexes. With the least bound electron principally localized on the metal, electron photodetachment produces neutral states that are best characterized by the atomic metal state plus a water molecule: [Cu (S-2), H2O], [Cu (D-2(5/2)), H2O], and [Cu (D-2(3/2)), H2O]. The large Cu--H2O separation gives rise to a remarkably narrow, isolated peak in the photoelectron spectrum, allowing an accurate, direct determination of the anion dissociation energy; when coupled with electronic structure calculations for the neutral, the adiabatic electron affinity is derived. (C) 2004 Elsevier B.V. All rights reserved.