Abstract: In this paper, the sorption of radionuclides on oxides, phosphates and clay minerals has been reviewed to clarify the different steps necessary to obtain reliable sorption data and tried to describe the usefulness of structural investigation at molecular level. The presentation mainly includes the following sections: (1) physicochemical characterization of sorbent’s structure and morphology; (2) the surface charge density of sorbent in aqueous solution; (3) the equilibrium constants of protonation and deprotonation on the sorbent’s surface; (4) the influences of pH, ionic strength and organic matters on the sorption behaviors of radionuclides; (5) the speciation and structure of radionuclides at solid-water interface; (6) surface complexation model and its application in evaluating the sorption mechanism of radionuclides; (7) the proofs from advanced spectroscopy technologies in this field.