The alkaline cooking of corn in a solution of Ca(OH)2 to produce corn-based foods is oriented to make corn proteins available, to incorporate Ca to the cooked grains, and also to remove the corn hull. This process (nixtamalization) is known in Mexico and Guatemala from prehispanic times; however, the effect of the alkaline cooking on the corn hull remains poorly documented. In this work, the physicochemical changes that take place in the corn hull during its cooking in a saturated solution of Ca(OH)2 were studied using infrared, X-ray diffraction, 13C cross-polarization/magic-angle spinning (CP/MAS) NMR, confocal imaging microscopy, differential scanning calorimetry, and thermogravimetry techniques. The main effect of this treatment on the hull is the removal of hemicelluloses and lignin, increasing the hull permeability and, as a consequence, facilitating the entry of the alkaline solution into the corn kernel. No significant changes were observed in the cellulose fiber network, which remains as native cellulose I, with a crystalline index, according to 13C CP/MAS NMR spectra, of 0.60. The alkaline treatment does not allow the cellulose fibers to swell and their regeneration in the form of cellulose(II). It seems any attempt to make use of the Ca binding capacity of the hull to increase the Ca availability in nixtamalized corn-based foods requires a separated treatment for the hull and kernel. On alkaline cooking, the hull hemicellulose fraction dissolves, losing its ability to bind Ca as a way to incorporate this element into foods elaborated from nixtamalized corn.