Ultrafine copper nanoparticles (Cu NPs) within porous silica nanospheres (Cu@SiO2) were prepared via a simple one-pot synthetic route in a reverse micelle system and characterized by SEM, TEM, EDX, XRD, N2 adsorption-desorption, CO-TPD, XPS, and ICP methods. The characterized results show that ultrafine Cu NPs with diameter of around 2 nm are effectively embedded in the center of well-proportioned spherical SiO2 NPs of about 25 nm in diameter. Compared to commercial SiO2 supported Cu NPs, SiO2 nanospheres supported Cu NPs, and free Cu NPs, the synthesized core-shell nanospheres Cu@SiO2 exhibit a superior catalytic activity for the hydrolytic dehydrogenation of ammonia borane (AB, NH3BH3) and hydrazine borane (HB, N2H4BH3) under ambient atmosphere at room temperature. The turnover frequencies (TOF) for the hydrolysis of AB and HB in the presence of Cu@SiO2 nanospheres were measured to be 3.24 and 7.58 mol H2 (mol Cu min)(-1), respectively, relatively high values for Cu nanocatalysts in the same reaction. In addition, the recycle tests show that the Cu@SiO2 nanospheres are still highly active in the hydrolysis of AB and HB, preserving 90 and 85% of their initial catalytic activity even after ten recycles, respectively.