A vapor deposition (VD) method was established for preparation of UiO-66 supported Fe (Fe/UiO-66) catalyst, which provided the first case of metal-organic framework (MOF) -supported Fe catalyst prepared by using vapor-based method. The Fe loading was around 7.0 ~8.5 wt% under present preparation conditions. The crystal structure of UiO-66 was not obviously influenced by the Fe loading, while the surface area significantly decreased, implicating most of the Fe components resided within the pores on UiO-66. The results for the methyl orange (MO) removal tests showed that MO in aqueous solution can be removed by UiO-66 by adsorption, and in contrast, it can be oxidized by H2O2 with the catalysis of Fe/UiO-66. Further catalytic tests showed that Fe/UiO-66 was rather effective to catalyze the oxidation of benzene derivatives like aniline in water in terms of chemical oxygen demand (COD) removal efficiency. The catalytic tests results for Fe/UiO-66 were compared to that of Fe/Al2O3 with a same Fe loading, as well as compared to the catalysts reported in the literature. This paper provides a general strategy for VD preparation of MOF-supported Fe catalyst on one hand, and new catalysts for removing organic pollutants from water on the other hand.