The arrangement of water molecules around a hydrated electron has eluded explanation for more than 40 years. Here we report sharp vibrational bands for small gas-phase water cluster anions, (H ₂ O) _4-6 ^– and (D ₂ O) _4-6 ^– . Analysis of these bands reveals a detailed picture of the diffuse electron-binding site. The electron is closely associated with a single water molecule attached to the supporting network through a double H-bond acceptor motif. The local OH stretching bands of this molecule are dramatically distorted in the pentamer and smaller clusters because the excited vibrational levels are strongly coupled to the electron continuum. The vibration–to–electronic energy transfer rates, as revealed by line shape analysis, are mode-specific and remarkably fast, with the symmetric stretching mode surviving for less than 10 vibrational periods [50 fs in (H ₂ O) ₄ ^– ].