There have been reports of ignition of high-pressure hydrogen during its sudden release for unexplained reasons and ignition mechanism still need to be further investigated. In this paper, mechanism of spontaneous ignition of high-pressure hydrogen during its sudden release into the L-shaped tube is investigated. LES, EDC model, 10-step like opening process of burst disk and 18-step detailed hydrogen combustion mechanism are employed. Three cases with burst pressures of 2.16, 6.21, and 9.10 MPa are simulated. It is found that shock wave is strongly reflected after it hits the tube corner wall, forming a reflected-shock-affected region and an energy conversion region with higher temperature, greater pressure and lower velocity. Afterwards, the reflected shock wave moving forward is reflected several times by the tube wall until it disappears and oblique shock is generated. After the hydrogen/air mixture enters the corner, it extends downstream along inner wall and separated from the main hydrogen/air mixture. The reflected shock wave moving backward interacts with the expansion waves and increases the temperature and pressure again, but spontaneous ignition cannot be initiated. Three mechanisms of spontaneous ignition of high-pressure hydrogen in the L-shaped tube are proposed eventually. The results reproduce the experimental spontaneous ignition conditions and positions, indicating that the numerical models can be applied as a tool for hydrogen safety engineering. (C) 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.