The conversion of organic pollutants to value-added chemicals has been considered as a sustainable approach to solve environmental problems. However, it is still a challenge to construct a suitable heterogeneous catalyst that can synchronously achieve the enrichment and activation of organic pollutants (such as 4-nitrophenol, 4-NP). Here, an organic-inorganic hybrid catalyst (CeO /Ni-MOF) was successfully fabricated for efficiently reducing 4-NP to 4-aminophenol (4-AP) with water as the hydrogen source. Based on the synergistic effect of Ni-MOF (adsorption action) and CeO (active sites), CeO /Ni-MOF could achieve a reaction rate of 1.102 μmol min mg with an ultrahigh Faraday efficiency (FE) (99.9%) and conversion (97.6%). In addition, the catalytic mechanism of 4-NP reduction over CeO /Ni-MOF was elaborated in depth. This work presents a new avenue for the effective reduction of pollutants and provides a new strategy for designing high-performance catalysts for rare-earth metals.