Designing highly efficient catalysts for use in fuel production is a highly attractive research area but still remains challenging. Herein, for the first time, ultrafine Ni nanoparticles (NPs) self-assembled on ceria nanowires (NWs) and then embedded in a microporous silica shell (denoted as Ni-CeO2@SiO2) are successfully designed and synthesized via a one-pot facile strategy. The average diameter of Ni-CeO2 NWs is just 2.9 nm, and the length is up to 102.7 nm. The resulting Ni-CeO2@SiO2 exhibits high performance and 100% hydrogen selectivity for H2 production from N2H4 and N2H4BH3 in aqueous solution. Unexpectedly, Ni-CeO2@SiO2 also has good catalytic performance and thermal stability for CO2 methanation. The high catalytic performance of Ni-CeO2@SiO2 can be attributed to the synergistic electronic effect and strong interaction between Ni NPs and CeO2 NWs with plenty of oxygen vacancies, as well as the unique structure effect. As an effective strategy, the present work provides an opportunity to embed ultrafine metal NPs-CeO2 NWs into a microporous silica shell, which has broad application prospects in various catalytic fields.