The article describes synthesis, crystal structure, ESI-MS and steady state and time-resolved fluorescence spectrum of a pentanuclear zinc(II) compound of composition [ZnII5(HL)2(μ3-OH)2(NO3)4] (1), where H3L is the [1 + 2] condensation product of 4-ethyl-2,6-diformylphenol and 2-amino-2-methyl-1-propanol. The phenol moiety and one of the two alcohol moieties of a H3L get deprotonated and therefore two ONO compartments of [HL]2− in 1 are inequivalent (O(alkoxide)N(imine)O(phenoxide) and O(alcohol)N(imine)O(phenoxide)). Each of the two compartments of each [HL]2− in 1 is occupied by a ZnII ion, to form a ZnII2 fragment. Two such fragments are linked by two μ3-hydroxide ligands to form a dimer-of-dinuclear type ZnII4 fragment. Each of the two alkoxide oxygen atoms bridges one ZnII in the ZnII4 fragment and a fifth ZnII ion (dangling metal ion) to form the pentanuclear system. The structure reveals that it is a new type of pentanuclear system among the related compounds. Notably, the pentanuclear moiety is retained in solution as evidenced from conductance measurement. The title compound exhibits fluorescence behaviour with the emission band at 447 nm on excitation at 384 nm. The quantum yield is 0.05. TCSPC reveals a monoexponential decay in 1. ESI-MS of 1 reveal the appearance of signals of positive ions corresponding to ZnII5, ZnII2 and ZnII metallic systems as well as to H3L ligand system.