Hydrogen gas has been considered as one of the promising sources of energy. Thus, several strategies including the hydrolysis of hydrides have been reported for hydrogen production. However, effective catalysts are highly required to improve the hydrogen generation rate. Two dimensional metal-organic frameworks (copper-benzene-1,4-dicarboxylic, CuBDC), and CuBDC-derived CuO@C were synthesized, characterized and applied as catalysts for hydrogen production using the hydrolysis and methanolysis of sodium borohydride (NaBH4). CuBDC, and CuO@C display hydrogen generation rate of 7620, and 7240 mlH2·gcat−1· min−1, respectively for hydrolysis. While, CuBDC offers hydrogen generation rate of 9060 mlH2·gcat−1· min−1 for methanolysis. Both catalysts required short reaction time, and showed good recyclability. The materials may open new venues for efficient catalyst for energy-based applications.