The novel catalyst with yolk-shell SiO2 NiMo/SiO2 spheres immobilized by zeolitic imidazolate framework (ZIF-67) materials has been successfully prepared. The experimental results indicated that the prepared catalyst exhibits superior performance for hydrogen generation from Formic acid (FA) dehydrogenation without any additives at low temperatures. The catalytic performances of the NixMo1−x/ZIF-67@SiO2 yolk-shell increased with Ni addition ratio increasing. In this research, Ni0.8Mo0.2/ZIF-67@SiO2 yolk-shell could provide the highest catalytic conversion efficiency. This is due to the uniform dispersion of fine metal nanoparticles (NPs) and synergistic effect between the NiMo NPs and ZIF-67@SiO2 supporter. The turn over frequency (TOF) value was approximately 13,183 h−1 at 25 °C through complete FA conversion. H2 selectivity was also approximately 100% with obvious CO-free hydrogen production at 25 °C. Meanwhile, the prepared NiMo/ZIF-67@SiO2 yolk-shell catalyst also shows superior catalytic stability with corresponding 99% activity after 10 cycles. In summary, the catalyst preparation and hydrogen generated from FA dehydrogenation obtained from this research could provide the important information for application in catalyst innovation and waste FA recycling and recovery in the future.