Semiconductor photocathodes with high quantum efficiency and low dark current are widely used in various vacuum photoelectric detection and imaging devices, such as photomultiplier tubes and image intensifiers, promoting the development of ultrafast detection and imaging technology for extremely weak light. Vacuum electron sources capable of producing high-quality electron beams are used in accelerator photoinjectors, electron microscopes, and other scientific equipment. First, this review introduces the classification of semiconductor photocathodes and their applications in the fields of vacuum photoelectric detection and imaging and vacuum electron sources. Then, preparation techniques for three types of typical semiconductor photocathodes, namely, alkali telluride, alkali antimonide, and GaAs photocathodes, are summarized. Subsequently, applications of new technologies, such as micro-nano structures, low-dimensional materials, and single-crystal epitaxy, in the development of semiconductor photocathodes are introduced. Finally, the technical development of the semiconductor photocathodes is discussed.