A sustainable and green catalytic strategy for C‐S coupling reactions is developed by combining micelle and transition metal. 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 FT‐IR, XPS, SEM, TEM, EDS, and ICP‐OES. The catalyst is recyclable and highly effective in mediating the conversion of halides to disulfides in water at room temperature with a broad substrate scope.