An interesting reversible, templated synthesis of unsymmetrical pyridine-ligated Zn complexes has been observed in solution and solid-state phases when Zn(salphen) complexes are reacted with methanol-substituted pyridine substrates. The X-ray molecular structure of an unusual Zn₃ supramolecular assembly is reported, in which the central Zn atom is embedded in a distorted octahedral geometry and each of the single anionic O atoms of the pyridine groups coordinates to a Zn(salphen) unit.