Anions of sodium, potassium, rubidium, and cesium are stable both in suitable solvents and in crystalline solids. The latter can be prepared either by cooling a saturated solution or by rapid solvent evaporation. Thermodynamic arguments show that alkali metal anions can probably exist in saturated solutions of the alkali metals in any compatible solvent, but that below saturation, dissociation into the cation and solvated electrons is favored in highly polar solvents such as ammonia. The key to solvent-free salts of the alkali metal anions is stabilization of the cation by incorporation into a suitable crown or cryptand complex. By using such complexes it also appears possible to produce “electride” salts in which the charge of the complexed cation is balanced by a trapped electron. The chemical, electrical, and optical properties of salts of the alkali metal anions and “electrides” could provide useful applications.