The successful preparation of organized porous inorganic fluorides (OPIFs) with a high specific surface area is demonstrated for MgF 2 . For the first time, macroporous MgF 2 OPIFs with a surface area of above 200 m 2 g −1 and mesoporous MgF 2 powder were prepared through the assembly of preformed MgF 2 nanoparticles and homemade polymer templates with a tunable size. These OPIF materials have been fully examined at different synthesis stages by means of powder X-ray diffraction, N 2 sorption, scanning electron microscopy, and transmission electron microscopy analyses and 19 F and 1 H solid-state nuclear magnetic resonance. The relation between the nature, the size, and the amount of polymer template on the porous structure was deeply investigated. The MgF 2 OPIFs present a higher thermal stability under air and F 2 calcination than MgF 2 nanoparticles as the structuration of the OPIF composite considerably slows down the crystallite growth during thermal treatment under air. OPIF materials were evaluated as heterogeneous catalysts for the fluorination of 2-chloropyridine under HF gas as a fluorinating agent at 350 °C. This study evidences catalytic sites with two Lewis acidity strengths (medium and low).