Numerical simulations have been carried out for spontaneous ignition of pressurized hydrogen release directly into air. Results showed a possible mechanism for spontaneous ignition due to molecular diffusion. To accurately calculate the molecular transport of species, momentum and energy in a multi-component gaseous mixture, a mixture-averaged multi-component approach was employed in which thermal diffusion is accounted for. To reduce false numerical diffusion, extremely fine meshes were used along with the ALE (Arbitrary Lagrangian-Eulerian) method. The ALE method was employed to track the moving contact surface with moving clustered grids. A detailed kinetic scheme with 21 elementary steps and 8 reactive chemical species was implemented for combustion chemistry. The scheme gives due consideration to third body reactions and reaction-rate pressure-dependant "fall-off" behavior. The autoignition of pressurized hydrogen release was previously observed in laboratory tests [2-3] and suspected as possible cause of some accidents. The present numerical study successfully captured this scenario. Autoignition was predicted to first take place at the tip region of the hydrogen-air contact surface due to mass and energy exchange between low temperature hydrogen and shock-heated air at the contact surface through molecular diffusion. The initial flame thickness is extremely thin due to the limiting molecular diffusion. The combustion region extends downward along the contact surface as it moves downstream. As the hydrogen jet developed downstream, the front contact surface tends to be distorted by the developed flow of the air. Turbulence plays an important role in mixing at the region of the distorted contact surface. This is thought to be a major factor for the initial laminar flame to turn into a final stable turbulent flame.