Metal–organic frameworks (MOFs) are promising candidates for room‐temperature hydrogen storage materials after modification, thanks to their ability to chemisorb hydrogen. However, the hydrogen adsorption strength of these modified MOFs remains insufficient to meet the capacity and safety requirements of hydrogen storage systems. To address this challenge, a highly defective framework material known as de‐MgMOF is prepared by gently annealing Mg‐MOF‐74. This material retains some of the crystal properties of the original Mg‐MOF‐74 and exhibits exceptional hydrogen storage capacity at above‐ambient temperatures. The MgO5 knots around linker vacancies in de‐MgMOF can adsorb a significant amount of dissociated and nondissociated hydrogen, with adsorption enthalpies ranging from −22.7 to −43.6 kJ mol−1, indicating a strong chemisorption interaction. By leveraging a spillover catalyst of Pt, the material achieves a reversible hydrogen storage capacity of 2.55 wt.% at 160 °C and 81 bar. Additionally, this material offers rapid hydrogen uptake/release, stable cycling, and convenient storage capabilities. A comprehensive techno‐economic analysis demonstrates that this material outperforms many other hydrogen storage materials at the system level for on‐board applications. A novel, highly defective Mg‐MOF‐74 is reported, featuring linker vacancies that enhance hydrogen chemisorption strength at neighboring MgO5 nodes. Consequently, defective metal‐organic framework (MOF) demonstrates the capacity to absorb significant amounts of dissociated and undissociated hydrogen at temperatures up to 160 °C. This approach is anticipated to expedite the utilization of MOFs in hydrogen storage applications.