A new ligand with N8O2 donors containing three potential metal-binding sites (H₂L) and its tricopper(II) complex 1 are synthesized. The tricopper species is found to be formed from a hypodentate dicopper(II) complex 2 in basic solutions. Complex 2 may be isolated from the reaction of H₂L with a copper source under acidic conditions. Complex 2 can undergo CO2-abstraction to yield an octacopper(II) complex 3. The single crystal structures of complexes 2 and 3 are characterized by X-ray crystallography.