Dolomite was treated at 800 °C (D800), characterized, and used in the adsorptive removal of catechol (1,2-dihydroxybenzene) from aqueous solutions. The performances of the D800 sample, named dolomitic solid, were compared with those of the raw material. A bibliographic review shows that the data on the adsorption of phenolic compounds by dolomites are non-existent. Kinetic data, equilibrium isotherms, thermodynamic parameters, and pH influence were reported. Special attention was paid to the spectroscopic study, before and after adsorption. The purpose was to understand the mechanism of catechol uptake on dolomitic materials. Kinetics follows the pseudo-second order model. The Redlich–Peterson isotherm provides the best correlation of our isotherms. Affinity follows the sequence: D800 ≫ raw dolomite. The process is spontaneous at low temperatures and exothermic. After catechol adsorption, the shape of the band in the 3,600−3,000 cm−1 range and its red shift towards 3,429 cm−1 reflect a deep involvement of OH groups both of D800 and catechol, which confirm hydrogen bonding via their respective OH. On this basis, a schematic illustration was proposed. The understanding of the phenolic compound–dolomitic solid interactions constitutes a fundamental approach to developing the application of these materials in wastewater treatment.