An analysis of the structures, some energy related properties, and key aspects of the bonding nature of the microsolvated electron with four water molecules is presented. The study is based on an exhaustive potential energy surface scan of the ground state of (H2O)4− at the UCCSD(T)/6-311(3+,4+)G(d,p)//UMP2/6-311(3+,4+)G(d,p) level. A total of 18 structures, most of them not reported before, spanning in an energy range of 8.8 kcal mol−1 were found. The energetic stability of the clusters is dictated by the effect of the excess electron on their structures, on their partial fragmentation, and on the hydrogen bonds’ framework. Vertical detachment energies depend on the number of water molecules holding the excess electron in “direct contact” to their two protons at the same time and, to a lesser extent, also depend on the hydrogen bond sequence in the rest of the structure. In general, hydrogen bonds in (H2O)4− are of closed shell character, and there are other less common interactions assisted by the excess electron.