Herein, a series of Fe-based catalysts have been designed and prepared by grinding a mixture of MIL-88d and melamine, and then the mixture was followed by pyrolysis. An unusual Fe/Fe3C-activated site is uniformly encapsulated in the N-doped carbon tubes obtained by pyrolysis of the film-like nanocrystals of MIL-88d. Experimental characterizations and theoretical calculations demonstrate that the surface N sites can effectively trap the nitrobenzene and aniline by their phenyl groups with the formation of three C-N bonds that made the catalyst exhibit excellent catalytic activity (turnover frequencies of <= 11268 h(-1) calculated on the basis of nitrobenzene) and chemoselectivity for the reduction of nitro derivatives under facile conditions.