Contact-electrification (CE) is a common phenomenon between any two materials or two phases of a material. But contact between two different materials may produce different outputs. When a p-type semiconductor slides on the surface of an n-type semiconductor, the current flowing between the two electrodes at the top of the p-type and the bottom of the n-type is a direct current. This phenomenon is called the “tribovoltaic effect” and was discovered in recent years. The mechanism of the tribovoltaic effect is the release of energy due to the formation of new chemical bonds at the interface by mechanical sliding; the energy released by which can excite electron-hole pairs at the PN junction, and the internal field established at the PN junction separates the electrons from the holes, resulting in a DC output. The energy released by the formation of chemical bonds is called the “bindington”, which acts as an internal exciton to excite the electron-hole pairs, similar to the photovoltaic effect. Here, we first review recent studies of the contact electrification involving semiconductors. Then, the mechanism of the tribovoltaic effect is introduced. Surface chemical methods to modulate the tribovoltaic effect are discussed. Finally, a hybrid tribovoltaic effect and its potential applications are described.