Fundamental understanding of tribochemical wear mechanism of oxide-free single crystalline silicon (without native oxide layer) is essential to optimize the process of ultra-precision surface manufacturing. Here, we report sliding speed-dependent nanowear of oxide-free silicon against SiO2 microspheres in air and in deionized water. When contact pressure is too low to induce Si yield, tribochemical wear occurs with the existence of water molecules and wear volume decreases logarithmically to constant as sliding speed increased. TEM and Raman observations indicate that the dynamics of rupture and reformation of interfacial bonding bridges result in the variation of tribochemical wear of the oxide-free Si with the increase of sliding speed.