The current study explores the potential of MgO-supported finite-sized TiMgn (n = 2–6) nanoclusters as hydrogen storage materials, employing density functional theory with a spin-polarized generalized gradient approximation (GGA). These systems' structural stability and electronic characteristics reveal that supported clusters offer superior hydrogen storage capabilities compared to their unassisted counterparts. Various parameters, including cluster-adsorption energy (Eads), hydrogen-adsorption energy in supported clusters (Eads-H), HOMO-LUMO gap, vertical ionization potential (VIP), vertical electron affinity (VEA), chemical potential (μ), and chemical hardness (ɳ) are computed. Substrate support notably enhances the thermodynamic stability and chemical reactivity of the TiMg5 cluster when contrasted with the bare TiMg5 cluster. Furthermore, a remarkable increase in the gravimetric hydrogen storage density, from 1.63 wt% for bare Mg5 clusters to 3.45 wt% for bare TiMg5 clusters, reaching 5.62 wt% in the supported TiMg5 cluster system is observed. These findings indicate the substrate-supported TiMg5 cluster as a promising candidate for hydrogen storage applications.