A surprising tribocatalytic capability has been discovered for Si single crystals to convert mechanical energy into chemical energy for organic dye degradation recently. In this study, their tribocatalytic capability has been explored for converting mechanical energy into chemical energy of water splitting. In glass reactors with Si single crystals coated on the bottoms and with H₂O and N₂ enclosed, Al₂O₃ nanoparticles, TiO₂ nanoparticles, and NiO particles were stimulated through magnetic stirring using home-made PTFE magnetic rotary disks separately. For Al₂O₃ nanoparticles, as much as 14,330 and 41,964 ppm H₂ were produced after 1 and 3 h of 400 rpm magnetic stirring, respectively, much higher than those obtained for TiO₂ and NiO, and for Al₂O₃ nanoparticles in glass-bottomed reactors as well. The tribocatalytic production of H₂ was further explored with respect to NaCl addition to H₂O and p/n doping in Si, with negative effects observed for them all. Photoluminescence spectroscopy revealed continuous generation of hydroxyl radicals in the course of magnetic stirring, which supports a tribocatalytic mechanism based on the excitation of electron–hole pairs in Si single crystals through mechanical energy absorbed through friction. These findings suggest a great potential for narrow-band semiconductors to utilize mechanical energy through friction to carry out important chemical reactions.