Reaction of 2-hydroxyimino-4,4-dimethy1-3-oxo-pentanenitrile (common abbreviation HPiCO, pivaloyl-cyanoxime) with zinc sulfate in an aqueous solution results in the formation of the two new complexes: [Zn(PiCO){H-(PiCO)(2)}(H2O)] (I) and tetranuclear Zn complex [Zn-4(mu(3)-OH)(2)(PiCO)(6) (H2O)(4)] (II). Both complexes were characterized by elemental analysis, IR- and UV-visible spectra, DSC/TGA studies, and X-ray analysis. In complex II, the PiCO(-) cyanoxime anion adopts three bidentate binding modes: O-monodentate, chelating (kappa(2)), and bridging (eta(2)) coordinations. Also, the ligand represents the mixture of two diasteromers (cis-anti and cis-syn) that form five- and six-membered chelate rings with Zn atoms and cocrystallize in one unit cell at population of 0.57-0.43. There are two crystallographically different Zn-centers in the ASU, and two mu(3)-bridging hydroxo-groups arrange via inversion center the formation of an elegant tetranuclear complex. Each Zn atom has a molecule of coordinated water and is in the distorted octahedral environment. Because of the structural flexibility and multidentate propensity of the pivaloyl-cyanoxime, complex II may act as a structural model of naturally occurring Zn-containing enzymes. Indeed, compound I exhibits an efficient catalytic performance for transesterification reaction of various esters in ethanol under mild reaction conditions. Therefore, obtained results allow assignment of observed activity as green catalysis.