This study evaluates the electrochemical hydrogen charging behavior and interaction between hydrogen and the microstructure of a duplex stainless steel. A saturation level of approximately 650 wppm is reached after 10 d of charging. The data are compared with a model resulting in a diffusion coefficient of 2.1 × 10−14 m2/s. A two-step increase of the concentration is observed and ascribed to saturation of ferrite followed by charging of austenite grains. Microstructural changes are observed during charging, i.e., formation and interaction of dislocations, as a result of the high residual stresses inherent to the production process of duplex stainless steels.