Hydrazine borane (HB; N2H4BH3) has been considered to be one of the most promising solid chemical hydrogen storage materials owing to its high hydrogen capacity and stability under ambient conditions. Despite that, the high purity of hydrogen production from the complete dehydrogenation of HB stands as a major problem that needs to be solved for the convenient use of HB in on-demand hydrogen production systems. In this study, we describe the development of a new catalytic material comprised of bimetallic Ni@Ir core-shell nanoparticles (NPs) supported on OMS-2-type manganese oxide octahedral molecular sieve nanorods (Ni@Ir/OMS-2), which can reproducibly be prepared by following a synthesis protocol including (i) the oleylamine-mediated preparation of colloidal Ni@Ir NPs and (ii) wet impregnation of these ex situ synthesized Ni@Ir NPs onto the OMS-2 surface. The characterization of Ni@Ir/OMS-2 has been done by using various spectroscopic and visualization techniques, and their results have revealed the formation of well-dispersed Ni@Ir core-shell NPs on the surface of OMS-2. The catalytic employment of Ni@Ir/OMS-2 in the dehydrogenation of HB showed that [email protected]/OMS-2 exhibited high dehydrogenation selectivity (>99%) at complete conversion with a turnover frequency (TOF) value of 2590 h(-1) at 323 K, which is the highest activity value among all reported catalysts for the complete dehydrogenation of HB. Furthermore, the [email protected]/OMS-2 catalyst enables facile recovery and high stability against agglomeration and leaching, which make it a reusable catalyst in the complete dehydrogenation of HB. The studies reported herein also include the collection of wealthy kinetic data to determine the activation parameters for [email protected]/OMS-2-catalyzed dehydrogenation of HB.