Direct evidence of hydrogen-assisted crack nucleation and propagation associated with the δ phase in the selective laser melted GH4169 superalloy was obtained. The analysis of hydrogen trapping sites using thermal desorption spectroscopy revealed that the δ phase exhibits strong hydrogen capture capability, with a hydrogen desorption activation energy of 35.45 ± 2.51 kJ/mol. In addition, spatially resolved hydrogen mapping conducted by scanning Kelvin probe force microscopy and hydrogen microprint technique provided further evidence for the δ phase as a deep hydrogen trapping site. The atomic-scale characterization sufficiently reveals the deformation mechanism of the δ phase induced by dislocation accumulation. Hydrogen-promoted dislocation slip localization facilitates the formation of microvoid defects in the δ phase, which is the main reason for the δ phase fracture, and induces intergranular and transgranular cracks.