A new Fe(III)/MOF-5(Ni) catalyst with high hydrostability was prepared using an equal load method under room temperature, and nearly 100% selectivity for catechol and 63.2% yield of dihydroxybenzene were obtained in hydroxylation of phenol with H 2 O 2 over Fe(III)/MOF-5(Ni) catalyst.A new Fe(III)/MOF-5(Ni) catalyst was prepared using an equal load method under room temperature. The Fe(III)/MOF-5(Ni) was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), Brunauer À Emmett À Teller (BET) measurements, infrared spectra (IR) and X-MaxN Energy spectrum. The results showed that by adding Ni into the [Zn 4 O] metal frame of MOF-5 to partially replace Zn, the formed metal coordination group [Ni 4 O(BDC) 3 ] enhanced the hydrostability of MOF-5(Ni).The catalytic activity was evaluated for phenol hydroxylation with hydrogen peroxide (30%). Compared with 2%Fe(III)/MOF-5, the yield of dihydroxybenzene greatly increased to 63.2% from 37% and the selectivity for catechol reached near 100% over 2%Fe(III)/ MOF-5(Ni)a with the Zn 2 + :Ni 2 + molar ratio 1:1, at lower reaction temperature 80°C, reaction time 2 h and catalyst to phenol mass ratio 0.053. It proved that the loading of both Ni and Fe 3 + into MOF-5 greatly increased the catalytic activity for the hydroxylation of phenol with hydrogen peroxide, and the plausible reaction mechanism of phenol hydroxylation with H 2 O 2 over Fe(III)/MOF-5(Ni) catalyst was also proposed.