The goal of this study is to obtain a deeper insight in the relation between hydrogen diffusion and hydrogen traps present in Armco pure iron. Cold deformation was applied to this material, which initially contained a limited amount of traps. The cold deformation was applied to increase the dislocation density and modify grain boundary characteristics. In this way, the hydrogen diffusivity decreased as the hydrogen trapping ability of the microstructure increased. A subsequent heat treatment allowed changing the density of microstructural defects again and consequently increased the hydrogen diffusion coefficient. In addition, studying blister formation showed that a higher degree of deformation caused more surface blisters, while recovery lowered the number of blisters. Electron backscatter diffraction characterisation provided the necessary input on the microstructural features and their evolution. Analysis of these samples allowed evaluating the correlation between hydrogen diffusion, blister formation and microstructural defects. This paper is part of a thematic issue on Hydrogen in Metallic Alloys