Over a core lifetime, the reactor materials Zircaloy-2, Zircaloy-4, and hafnium may become embrittled due to the absorption of corrosion-generated hydrogen and neutron irradiation damage. Results are presented on the effects of fast fluence on the fracture toughness of: (1) wrought Zircaloy-2, Zircaloy-4, and hafnium; (2) Zircaloy-4 to hafnium butt welds; and (3) hydrogen-precharged beta-treated and weld-metal Zircaloy-4 for fluences up to a maximum of approximately 150 × 1024 n/m2 (>1 MeV). While Zircaloy-4 did not exhibit a decrement in KIC due to irradiation, hafnium and butt welds between hafnium and Zircaloy-4 are susceptible to embrittlement with irradiation. The embrittlement can be attributed to irradiation strengthening, which promotes void formation in the high-strain crack-tip region, and, in part, to the lower chemical potential of hydrogen in Zircaloy-4 compared to hafnium, which causes hydrogen to drift over time from the hafnium end toward the Zircaloy-4 end and to precipitate at the interface between the weld and base-metal interface. Neutron radiation apparently affects the fracture toughness of Zircaloy-2, Zircaloy-4, and hafnium in different ways. Possible explanations for these differences are suggested. It was found that Zircaloy-4 is preferred over Zircaloy-2 in hafnium-to-Zircaloy butt-weld applications due to absence of a radiation-induced reduction in KIC plus its lower hydrogen absorption characteristics compared with Zircaloy-2.