The tribovoltaic effect is a phenomenon where direct voltage and current are generated through mechanical friction on semiconductor interfaces, offering a new energy conversion mechanism by coupling semiconductor and triboelectrification. This effect was first proposed in 2019 and has since developed into various forms of tribovoltaic nanogenerators (TVNGs), including metal-semiconductor, metal-insulator-semiconductor, semiconductor-semiconductor, liquid-solid, and flexible interfaces. Compared to triboelectric nanogenerators (TENGs), TVNGs exhibit characteristics such as direct current, high current density (mA·A cm⁻²), and low impedance (Ω–kΩ). Two main mechanisms for the tribovoltaic effect have been identified: one dominated by built-in electric fields and the other by interface electric fields. The tribo-photovoltaic and tribo-thermoelectric effects have also been discovered, as they can interact with other multi-physical field effects. TVNGs are suitable for energy harvesting and self-powered sensing devices in micro-nano energy applications. This paper reviews the development of the tribovoltaic effect, discusses its mechanisms, and explores future research directions, aiming to accelerate the development of smart wearable electronics and intelligent industrial components. The tribovoltaic effect was first observed at the metal-semiconductor interface in 2018, with Liu et al. reporting DC output from sliding a metal probe on a MoS₂ film. In 2019, Wang et al. coined the term "tribovoltaic effect," similar to the photovoltaic effect. Xu et al. confirmed the tribovoltaic effect and discovered its photovoltaic coupling effect in Si interfaces. Zhang et al. formally defined the tribovoltaic effect as the generation of direct voltage and current by mechanical friction on semiconductor interfaces and proposed a coupling power generation mechanism with the thermoelectric effect. Lin et al. achieved DC power generation from liquid-solid friction, and Song et al. observed DC output from a metal tip sliding on ZnO nanowires. Meng et al. developed an organic TVNG based on flexible interfaces, broadening its application in wearable electronics. Huang et al. investigated a structural superlubric TVNG based on graphene with a micro-lamellar structure. Zheng et al. explored TVNG performance under low temperatures, noting improvements in performance as temperature decreased. In 2022, Zhang et al. proposed a mechanism based on interfacial electric fields, realizing high-performance TVNGs with ultra-high voltage and power density. Qiao et al. enhanced TVNG wear resistance using water-based graphene. Yuan et al. designed a rolling-mode TVNG for mechanical and solar energy harvesting. Yang et al. realized the transition of Vanadium oxide from metal to semiconductor phase, enabling controllable output tuning. Deng et al. fabricated tribovoltaThe tribovoltaic effect is a phenomenon where direct voltage and current are generated through mechanical friction on semiconductor interfaces, offering a new energy conversion mechanism by coupling semiconductor and triboelectrification. This effect was first proposed in 2019 and has since developed into various forms of tribovoltaic nanogenerators (TVNGs), including metal-semiconductor, metal-insulator-semiconductor, semiconductor-semiconductor, liquid-solid, and flexible interfaces. Compared to triboelectric nanogenerators (TENGs), TVNGs exhibit characteristics such as direct current, high current density (mA·A cm⁻²), and low impedance (Ω–kΩ). Two main mechanisms for the tribovoltaic effect have been identified: one dominated by built-in electric fields and the other by interface electric fields. The tribo-photovoltaic and tribo-thermoelectric effects have also been discovered, as they can interact with other multi-physical field effects. TVNGs are suitable for energy harvesting and self-powered sensing devices in micro-nano energy applications. This paper reviews the development of the tribovoltaic effect, discusses its mechanisms, and explores future research directions, aiming to accelerate the development of smart wearable electronics and intelligent industrial components. The tribovoltaic effect was first observed at the metal-semiconductor interface in 2018, with Liu et al. reporting DC output from sliding a metal probe on a MoS₂ film. In 2019, Wang et al. coined the term "tribovoltaic effect," similar to the photovoltaic effect. Xu et al. confirmed the tribovoltaic effect and discovered its photovoltaic coupling effect in Si interfaces. Zhang et al. formally defined the tribovoltaic effect as the generation of direct voltage and current by mechanical friction on semiconductor interfaces and proposed a coupling power generation mechanism with the thermoelectric effect. Lin et al. achieved DC power generation from liquid-solid friction, and Song et al. observed DC output from a metal tip sliding on ZnO nanowires. Meng et al. developed an organic TVNG based on flexible interfaces, broadening its application in wearable electronics. Huang et al. investigated a structural superlubric TVNG based on graphene with a micro-lamellar structure. Zheng et al. explored TVNG performance under low temperatures, noting improvements in performance as temperature decreased. In 2022, Zhang et al. proposed a mechanism based on interfacial electric fields, realizing high-performance TVNGs with ultra-high voltage and power density. Qiao et al. enhanced TVNG wear resistance using water-based graphene. Yuan et al. designed a rolling-mode TVNG for mechanical and solar energy harvesting. Yang et al. realized the transition of Vanadium oxide from metal to semiconductor phase, enabling controllable output tuning. Deng et al. fabricated tribovolta