Two MOF-supported Mo(VI) oxidation catalysts bearing N,O-chelating ligand were synthesized via dative and covalent-dative postsynthetic modifications of a two-fold interpenetration pillared-layer aminefunctionalized MOF known as TMU-16-NH2. These post-functionalized catalysts were characterized by FT-IR spectroscopy, thermogravimetric analysis, ICP and X-ray powder diffraction techniques. The Mo(VI)-containing MOFs exhibit both epoxide selectivity and fully reusability for alkenes epoxidation by tert-butylhydroperoxide (TBHP).