The phenomenon of structural transformation in metal-organic frameworks (MOFs), characterized by a phase transition from one structure to another through the dissociation and recombination of coordination bonds, is well recognized. In this study, we successfully developed a new structural transformation from MIL-101(Cr) to MIL-53(Cr) using fluoride as an additive. In addition, the structural transformation proceeds without additives in the case of MIL-101(Cr) with electron-withdrawing groups. To our knowledge, this is the first example of a structural transformation system using kinetically inert Cr-based MOFs.