Successful synthesis and investigation of a new material that uses copper-metal–organic frameworks (Cu-MOFs) as the template for loading LiBH₄ are reported. The nanoconfinement of LiBH₄ in the pores of Cu-MOFs results in an interaction between LiBH₄ and Cu²⁺ ions, enabling the LiBH₄@Cu-MOFs system to achieve a much lower dehydrogenation temperature than pristine LiBH₄.