Rapid coupling reactions between 2,6-bis(azidomethyl)pyridine and terminal alkynes in the presence of 5 mol% Cu(OAc)2·H2O without the addition of a reducing agent afford tridentate ligands for first-row transition-metal ions. The chelation between CuII and alkylated nitrogen atoms of the azido groups of 2,6-bis(azidomethyl)pyridine, as observed in the solid state, is credited for the acceleration of the azide–alkyne cycloaddition reactions.