<p>Hydrogen carriers that enable efficient transport and on-demand release of molecular hydrogen (H<sub>2</sub>) are crucial for practical hydrogen-based energy systems. Hydrogen boride (HB) nanosheets, composed of boron and hydrogen in a 1:1 stoichiometric ratio, have promising potential as safe and lightweight hydrogen carriers owing to their high gravimetric hydrogen density (8.5 wt %). In particular, heating of HB nanosheets results in H<sub>2</sub> release over a broad temperature range from 423 to 1473 K. However, the mechanism of the multimodal H₂ desorption remains unclear. In this work, we elucidate that the interlayer H···H distances (dH···H) determine the multimodal desorption of H<sub>2</sub> especially in the lower-temperature range (< 623 K). HB nanosheets subjected to various temperatures under different H<sub>2</sub> pressures were prepared to investigate the thermal stability of their bonding configurations. Infrared spectroscopy and temperature-programmed desorption measurements revealed the occurrence of hydrogen depletion while the bonding configuration remains unchanged. The first to third nearest dH···H, along with the numbers of the corresponding H···H pairs, were systematically calculated for four possible interlayer stacking types. The calculated H···H pairs distribution closely matched the experimental profile for the thermally induced H<sub>2</sub> desorption, suggesting that the multimodal desorption of H<sub>2</sub> in the lower-temperature range is governed by the distribution of hydrogen distances. This study elucidates the unique mechanisms of H<sub>2</sub> formation in HB nanosheets and provides valuable insights into the design of two-dimensional hydrogen containing materials.</p>
