Metallo-supramolecular core cross-linked (CCL) micelles are fabricated from terpyridine-functionalized double hydrophilic block copolymers, poly(2-(2-methoxyethoxy)ethyl methacrylate)-b-poly(2-(diethylamino)ethyl methacrylate-co-4-(6-methacryloxyhexyloxy)-2,2:6,2-terpyridine) [PMEO2MA-b-P(DEA-co-TPHMA)] via the formation of bis(terpyridine)ruthenium(II) complexes. These metallo-supramolecular CCL micelles exhibit not only high structural integrity under different pH values and temperatures in aqueous solution, but multistimuli responsiveness including pH-responsive cores, thermo-responsive shells, and reversible dissociation of bis(terpyridine)ruthenium(II) complexes upon addition of competitive metal ion chelator, which allows for precisely controlled release of the encapsulated hydrophobic guest molecules via the combination of different stimuli.