With the development of hydrogen economy, the demand of structural materials with high strength suitable for service in hydrogen or hydrogen-bearing environments such as storage of hydrogen gas was incremental. An optional structural materials is J75 alloy, which is mainly strengthened by an ordered fcc γ' phase, Ni₃(Al, Ti), coherent with the austenite matrix. Investigation on J75 alloy indicated that the commercial alloy free of B would lose about half its ductility when charged with hydrogen, accompanied by a change of fracture mode from ductile rupture to brittle-appearing intergranular fracture. Otherwise, an improvement in ductility and hydrogen resistant performance was observed in the J75 alloy with trace B, however, its role in the alloy is unclear. So, in present work, mechanism of B in the J75 hydrogen-resistant alloy was investigated by means of OM, SEM, TEM, EPMA, 3DAP, SIMS, hydrogen penetration, thermal hydrogen charging experiments and tensile tests. It was found that a lot of Ti segregated at grain boundaries (GBs) in the alloy free of B, resulted in abundant precipitation of cellular η phases. However, the cellular η phase was not observed in the alloy with B, and it could be attributed to the segregation of B atoms at GBs and inhibited the segregation of Ti. A lower hydrogen diffusion coefficient was observed in the alloy with B than that in the alloy free of B by hydrogen permeation, indicating that diffusion velocity of H atoms in the alloy had been decreased by the addition of B. Moreover, segregation of B at GBs could not only inhibit the precipitation of η phases but also decrease the number of H atoms there, which would improve the hydrogen-resistant performance of the alloy.