We report the discovery and photoelectron spectroscopic study of the four double Rydberg anions: N2H7−, N3H10−, N4H13−, and N5H16−; of three solvated double Rydberg anions; and of a previously unseen feature in the spectrum of the double Rydberg anion, NH4−. In each case, vertical detachment energies were measured and vibrational features tentatively assigned. In the case of solvated double Rydberg anions, anion–neutral interaction energies were also determined.