A novel Ce(IV)-anchored L-leucine covalently bonded to mesoporous MCM-41 has been synthesized by a non-hydrothermal post-functionalization approach. It has been thoroughly characterized by sophisticated physicochemical techniques. The material was applied in the efficient green synthesis of aromatic sulfides by C–S coupling using molecular sulfur and haloarenes. Another catalytic application was in the synthesis of symmetric disulfides by the homocoupling of aromatic thiols in the presence of H₂O₂ as an oxidant. The ligand-free protocol is simple, clean and free from hazardous chemicals. Moreover, the catalyst is reusable for several times, thus making the methodology sustainably viable.