Hierarchical porous Hβ molecular sieve was obtained by alkaline treatment of NaOH solution for Hβ molecular sieve. Fe-hierarchical porous Hβ molecular sieve was prepared by impregnation method under the condition of 0.1 mol/L alkali concentration. The samples were characterized by XRD, XRF, N2 adsorption-desorption, SEM-EDS, Fourier transform infrared spectroscopy, NH3-TPD and Py-FTIR. The results showed that the samples with the proper alkali concentration treatment could maintain the microporous framework of Hβ molecular sieve while mesopore was introduced. Fe-hierarchical porous Hβ molecular sieve also could maintain the micro-mesoporous structure, and the active component Fe2O3 could be well dispersed on the surface of the carrier. The benzene and benzyl chloride were used to investigate the performance of Fe-hierarchical porous Hβ in the synthesis of diphenylmethane reaction. Compared with the Fe-Hβ catalyst, Fe-hierarchical porous Hβ effectively improved the diffusion performance of the reactants and products. The conversion of benzyl chloride and the selectivity of diphenylmethane increased by 9.4% and 3.2%. In the meantime, the catalyst showed excellent anti-deactivation ability.