The assembly formation of Zn cluster compounds comprising pyridinealcohol ligands is described and their solution and solid state features have been determined using NMR spectroscopy and X-ray diffraction. The di-Zn complex 5 and tetra-Zn complex 7 may serve as accessible structural models for the active site of various multinuclear Zn-containing metalloenzymes. Their phosphoester cleavage activity was tested and correlated with their dynamic structural features.