Hydrogen embrittlement (HE) extant a substantial concern to press-hardened steel (PHS) owing to superior strength. The high strength to light-weight automobile structures necessitates the advancement of superior HE resistance PHS. This study investigated the HE susceptibility of Nb-microalloyed PHS by slow strain rate tensile testing, u-shaped constant bending load test, and thermal desorption spectroscopy. Nb enhances microstructure and HE resistance by introducing retained austenite, refining prior austenite grains (21.14–13.73 μm), forming low-angle grain boundaries, and nano-scale precipitates. Nb-alloyed steel exhibits no-cracking over 300 h under high pre-bending stress and decreases elongation loss up to 48% in hydrogen environment as compared to Nb-free steel. Diffusible H-content in 0.12 wt% Nb-steel reduces to 14.9% of that in Nb-free steel owing to enhanced hydrogen traps, the Fcc/Bcc matrix, and carbide precipitation. The multi-phase microstructure with nano-scale NbC precipitation impeded the localized H-dispersion, enhancing the HE resistance in PHS despite its high strength.