Unique self-assembled macrocyclic multinuclear ZnII and NiII complexes with binaphthyl-bipyridyl ligands (L) were synthesized. X-ray analysis revealed that these complexes consisted of an outer ring (Zn3L3 or Ni3L3) and an inner core (Zn2 or Ni). In the ZnII complex, the inner Zn2 part rotated rapidly inside the outer ring in solution on an NMR timescale. These complexes exhibited dual catalytic activities for CO2 fixations: synthesis of cyclic carbonates from epoxides and CO2 and temperature-switched N-formylation/N-methylation of amines with CO2 and hydrosilane.