A dual-metal catalysis system including a newly prepared nanoparticle [SiO₂@organic-linker(OL)@Pd^(II)] and CuI was introduced with ultra-high catalytic activity (high turnover number (TON), up to 19 000) to a one-pot and odorless synthesis of unsymmetrical aryl sulfides by crossover C–S bond formation. The reaction proceeds via C–O bond activation of phenols and direct C–S bond formation in the presence of S₈ as an oddorless sulfur source and aryl boronic acids under mild conditions (room temperature). The catalyst could be recycled up to five times without an obvious change in its activity.