Diquite (D) and bentonite (B) mineral samples from the Amazon region, Brazil, were modified by MTTZ derivative (5-mercapto-1-methyltetrazole) using heterogeneous route. These materials were characterized by textural and elemental analysis, transmission electron microscopy (TEM), power X-ray diffraction and 13C NMR spectroscopy. The chemically modified clay (D MTTZ and B MTTZ) samples showed modification of its physical–chemical properties including: specific area 41.4 (B) to 398.5 m 2 g −1 (B MTTZ) and 25.0 (D) to 178.8 m 2 g −1 (D MTTZ). The adsorption experiments performed under batch process with Th(IV) concentration, pH and contact time as variables. The ability of these materials to remove thorium from aqueous solution was followed by a series of adsorption isotherms adjusted to a Sips equation at room temperature and pH 2.0, with variable concentration of Th(IV). The maximum number of moles adsorbed was determined to be 10.45 × 10 −2 and 12.76 × 10 −2 mmol g −1 for D MTTZ and B MTTZ, respectively. The energetic effects (Δ int H°, Δ int G° and Δ int S°) caused by thorium cation adsorption were determined through calorimetric titrations.