Semiconductors with negative electron affinity (NEA) surfaces are used as photoemitters, secondary emitters, and cold-cathode emitters. A comprehensive review of the characteristics and applications of these materials is presented, the concept of NEA is described, and a comparison is made between NEA and conventional emitters. Electron generation, transport, and emission processes of NEA emitters are discussed. NEA III-V compound photocathodes, especially GaAs, are described with respect to their fabrication, performance, and applications to photomultipliers and image intensifier tubes. The structure and performance of NEA secondary emitters are presented. NEA GaP secondary-emission dynodes represent the most important device application. NEA cold cathodes, using GaAs, Ga(As, P), or Si, have been investigated, and their performance characteristics are summarized. NEA Si cold cathodes have been incorporated in developmental TV camera tubes. The characteristics of these tubes are reviewed.