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The hydrogen distribution of 16MnR steel weldment in hydrogen contained environment was calculated using the finite element method (FEM). The effect of welding residual stress on hydrogen diffusion has been discussed using a 3-D sequential coupling finite element analysis procedure complied by Abaqus code. The hydrogen diffusion coefficient in weld metal, the heat affected zone (HAZ), and the base metal of the 16MnR steel weldment were measured using the electrochemical permeation technique. The hydrogen diffusion without the effect of stress was also calculated and compared. Owing to the existence of welding residual stress, the hydrogen concentration was obviously increased and the hydrogen would diffuse and accumulate in the higher stress region.