Lithium borohydride (LiBH) has received much attention due to its high hydrogen density of 18.5 wt%. However, in the hydrolytic process for hydrogen supply, the sluggish kinetics of LiBH and the agglomeration of by-product greatly limit its wide utilization. In this work, transition-metal chlorides (CoCl, NiCl, FeCl) are firstly adopted to explore the hydrogen liberation behaviors of LiBH. The hydrolysis kinetics can be well-controlled by tuning the concentration of chlorides. Among the above chlorides, CoCl displays much faster reaction kinetics, delivering a hydrogen generation rate ranging from 421 to 41701 mL min g with a maximum conversion of 95.3%, much higher than the value of 225 mL min g H with Pt–LiCoO. The maximum gravimetric hydrogen density may reach 8.7 wt% at HO/LiBH = 2–6 mol/mol. Furthermore, NH is introduced to solve the issue of uncontrollable kinetics of LiBH by forming its ammoniates, where LiBH·NH catalyzed by CoCl could stably release over 4350 mL g H per unit weight of LiBH within 30 min at 40 °C, with a hydrogen density of ∼7.1 wt% and a hydrogen yield of 97.0%. Our approaches adopting non-noble metal chlorides are efficient and affordable for hydrogen supply to PEMFCs via hydrolysis of LiBH-based materials.