The present invention relates to an alkali metal generating agent and others for formation of a photo-cathode or a secondary-electron emitting surface capable of stably generating an alkali metal. The alkali metal generating agent is used in formation of a photo-cathode for emitting a photoelectron corresponding to incident light, or in formation of a secondary-electron emitting surface for emitting secondary electrons corresponding to an incident electron. Particularly, the alkali metal generating agent contains at least an oxidizer comprising at least one vanadate with an alkali metal ion as a counter cation, and a reducer for reducing the ion. An alkali metal generating device comprises at least the alkali metal generating agent and a case housing it, and the case is provided with a discharge port for discharging the vapor of the alkali metal.