The enzymatic inhibition promoted by hypervalent species of selenium and tellurium is widely known in the literature. Thereby this work brings new perspectives for a more detailed study of the interaction between chalcogenides with thiols. To achieve this goal, it was synthesized two different classes of organochalcogenides derived from 4-(phenyltellanyl)benzaldehyde (class I and class II). Furthermore, the preparation route of the class I (no cationic ligand) ligands involved a six-step synthetic sequence in overall yields of 26% and 19%, and the Class II (cationic ligand) ligands were prepared in a two-step sequence in global yields of 43% and 22% of the selenides and tellurides, respectively. After synthesis, the ligands contain a phenylchalcogenide moiety, a polyether spacer group functionalized with an amino group to attach it to an agarose substrate, was immobilization on to agarose as ligands in affinity chromatography affinity technique, and finally, it was demonstrated that organochalcogenide-modified agarose is a new class of functional materials for the retention and release of biothiols presenting a "catch & release" functionality