A sustainable and green catalytic strategy for C-S coupling reactions is developed by combining micelle and transition metal catalysis. The synergistic AGA8@Cu(I) catalyst forms by spontaneous anchoring of the in-situ generated Cu(I) nanoclusters onto the AGA8 micelles, and has been fully characterized by XPS, FT-IR, and TEM. The catalyst is highly effective and recyclable in mediating the conversion of halides to disulfides in water at room temperature with a broad substrate scope.