The effects of alkaline treatment on the mesoporosity development and iron speciation in Fe−MFI zeolites have been investigated. To this end, a variety of samples derived from different synthetic routes and having distinct Si/Al ratios and Fe content were treated in NaOH solutions and characterized by N2 adsorption, SEM, TEM, UV/vis spectroscopy, and EPR. The alkaline treatment induces a significant intracrystalline mesoporosity development by framework silicon extraction and promotes disintegration of oligomeric iron species. Iron in framework positions has shown to provoke mesopore formation, whereas nonframework iron species suppresses silicon leaching and lowers the extent of extra porosity.