This study focused on the structure and physical properties of acid-treated bentonite L45 from the Lieskovec deposit (Slovakia). New applications of near infrared and visible spectroscopies were used to follow Fe-montmorillonite dissolution and layer-charge reduction. Progressive dissolution of L45 results in the formation of a protonated amorphous silica phase. The OH overtone at 7312 cm–1 revealed the creation of Si–OH groups in the mildly treated samples. The area of the Si–O–M
oct band, as obtained by a peak-fitting procedure, is a sensitive indicator of the changes in the octahedral sheets. Ultraviolet-visible (UV-VIS) spectroscopy of the smectite dispersions with methylene blue (MB) is an efficient method for controlling the acid activation process of bentonites. The results reveal that acid treatment causes a substantial layer-charge reduction, probably due to prevailing dissolution of MgO4(OH)2 polyhedra in the octahedral sheets. The layer-charge reduction is proportional to the structural changes and to the extent of mineral decomposition upon acid treatment.