Recently, developing a cost-effective and high-performance catalyst is regarded as an urgent priority for hydrogen generation technology. In this work, ISOBAM-104 stabilized Co/Fe colloidal catalysts were prepared via a co-reduction method and used for the hydrogen generation from KBH4 hydrolysis. The obtained ISOBAM-104 stabilized Co10Fe90 colloidal catalysts exhibit an outstanding catalytic activity of 37,900 mL-H2 min−1 g-Co−1, which is far higher than that of Fe or Co monometallic nanoparticles (MNPs). The apparent activation energy (Ea) of the as-prepared Co10Fe90 colloidal catalysts is only 14.6 ± 0.7 kJ mol−1, which is much lower than that of previous reported noble metal-based catalysts. The X-ray photoelectron spectroscopy results and density functional theory calculations demonstrate that the electron transfer between Fe and Co atoms is beneficial for the catalytic hydrolysis of KBH4.