Ab initio molecular dynamics simulations and first-principles calculations reveal the existence of a solvated dielectron species, (2e)(s), in an LiF ionic matrix. The nature of the solvation mechanism and the stability of the species was explored. In addition to electrostatic interactions, a hole-orbital coupling. among solvent molecules may significantly enhance the stability of the solvated electrons and govern the extent of electron solvation. This hole-orbital coupling is different from either an electrostatic coupling or conventional chemical bonding, and it may be described as a transition between them.