The effect of various experimental conditions (i.e., hydrogen charging current density, charging time, solution concentration, and temperature) on the embrittlement and cracking susceptibility of 2205 duplex stainless steel was studied by electrochemical hydrogen charging and slow strain rate tests. The results showed that the choice of the experimental conditions had obvious effect on the hydrogen concentration in the specimens. A relationship between the embrittlement and hydrogen charging conditions was established by the investigation of the fracture morphology. Under the free-charging condition, the fracture surfaces were characteristic of dimples, while on the condition of the dynamic hydrogen charging, the hydrogen-induced fracture showed the appearance of cleavage. Further examination of fracture cracks confirmed that the ferrite phase acts as a preferential path for crack propagation.