The electronic structure of Ag2Te has been investigated, theoretically using the self-consistent full-potential linear-muffin-tin-orbital (LMTO) calculation, and experimentally using photoelectron spectroscopy. Comparison of the calculated and measured photoemission data shows, in general, good agreement. Based on the total energy calculations performed for several model structures, the stability of the tetrahedral and octahedral Ag coordinations is examined. It is found that the alpha - beta phase transition is ascribed to the energy lowering accompanying the Ag coordination change and the atomic displacements in the beta-Ag2Te. The fast-ionic diffusion paths of Ag atoms in the high temperature phase are also discussed.