Nb alloying has been reported to deteriorate the hydrogen embrittlement resistance of multiphase steels, which contrasts to the case of single-phase metallic materials. This study clarifies the impact of Nb alloying on the hydrogen embrittlement behaviour of a novel multiphase stainless steel. The findings revealed a 17 % reduction in the hydrogen embrittlement sensitivity upon Nb incorporation. It was found that higher austenite fractions in the Nb-bearing steels impeded hydrogen ingress. The austenite phase in such Nb-bearing steels possesses a higher stacking fault energy, thereby delaying martensitic transformation and crack initiation. The precipitation of nanometre-sized NbC in the matrix obstructed hydrogen diffusion, which indirectly inhibited crack initiation and propagation.