The aim of this study is to gain an insight into the physical phenomena underlying the spontaneous ignition of hydrogen following a sudden release from high-pressure storage and transition to sustained jet fire. The modelling and large-eddy simulation (LES) of the spontaneous ignition dynamics in a tube with a non-inertial rupture disk separating the high-pressure hydrogen storage and the atmosphere is described. Numerical experiments confirmed that due to the stagnation conditions a chemical reaction first commences in the tube boundary layer, and subsequently propagates throughout the tube cross-section. The dynamics of flame formation outside the tube, simulated by the LES model, has reproduced the combustion patterns, including vortex induced “flame separation”, which have been experimentally observed by high-speed photography. It is concluded that the LES model can be applied for hydrogen safety engineering, e.g. for the development of innovative pressure relief devices.