The effect of hydrogen on the deformation and fracture behavior in pure Cu, pure Ni and Cu–Ni alloy was studied via tensile tests of H-charged, smooth and circumferentially-notched specimens at room temperature (RT) and 77 K. Hydrogen-diffusion properties were determined by the desorption method. To obtain a uniform hydrogen concentration in the H-charged specimens, specimens were exposed to 100-MPa hydrogen gas at 543 K for 200 h, based on the determined hydrogen diffusivity. In tensile tests of smooth pure Ni and Cu–Ni alloy specimens at RT, common hydrogen effects were detected, namely, an increase in yield and flow stresses — a hardening effect; and a ductility loss that was accompanied by a change in fracture surface from ductile to brittle feature — an embrittling effect. With regard to the embrittling effect, the pure Ni and Cu–Ni alloy showed different fracture-surface morphologies at RT; the pure Ni showed an intergranular (IG) surface and the Cu–Ni alloy surface was flat. However, a number of IG cracks were detected beneath the fracture surfaces on the smooth Cu-Ni alloy. The tensile tests of the H-charged smooth specimens at 77 K yielded an IG surface for the pure Ni and a ductile fracture surface with dimples in the Cu–Ni alloy. In contrast, tensile tests of the H-charged, notched specimens at RT demonstrated clear IG fractures for the pure Ni and Cu–Ni alloy. These facts indicate that IG cracking was the first step in the embrittling process for the pure Ni and Cu–Ni alloy, and IG cracking was accompanied by a large plastic deformation that formed the flat surface (unclear IG surface) for the smooth Cu–Ni alloy. Considering that the HE of both pure Ni and Cu–Ni alloy was related to IG cracking, possible mechanisms were discussed and tensile tests performed at 77 K suggested two possibilities: (I) interaction between hydrogen-moving dislocation is more important in the HE process of the Cu-Ni alloy compared to the pure Ni; (II) hydrogen transportation towards grain boundaries are required to cause the IG fracture in the Cu-Ni alloy.