The tribovoltaic devices have demonstrated an enormous current density output from friction. This has attracted attention, and thus, the tribovoltaic device research is expected to grow rapidly, providing mechanical energy harvesting from human motion or mechanical vibrations to power the microdevices. Herein, we are demonstrating the novel tribovoltaic device based on the W/WO3 Schottky junction enabled by high-energy electrons as in hot-carrier photovoltaic devices. The hot carrier injection from the metal to the semiconductor has been well demonstrated before in light-driven devices but not demonstrated for tribovoltaic devices. Friction-caused electronic excitations on the W needle provide energy for electrons to overcome the Schottky barrier and generate the unbiased current density up to 1270 A m−2 . The amorphous WO3 derived from magnetron sputtering shows high durability and reliability of the tribovoltaic device.