New hexanuclear zinc complex, Zn-6(OAc)(8)(mu-O)(2)(dmae)(4) (1) (OAc = acetato, dmae = N,N-dimethyl aminoethanolato) has been synthesized and characterized by its melting point, elemental analysis, Fourier transform infrared spectroscopy, atmospheric-pressure chemical-ionization mass spectrometry, thermal gravimetric analysis, and single crystal X-ray analysis. The complex (1) crystallizes in the monoclinic space group C2/c. The high solubility of complex (1) in organic solvents such as alcohol, THF, and toluene and low decomposition temperature as compared to Zn(OAc)(2) make it a promising single source candidate for the deposition of nanostructured ZnO thin films by aerosol-assisted chemical vapor deposition. Films with various nanostructures, morphology, and crystallographic orientation have been deposited by controlling the deposition temperature. The deposited films have been characterized by X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray analysis. The optical characterization of ZnO films deposited on the FTO substrate show a direct band gap of 3.31 eV, and the photoelectrochemical study revealed that the photocurrent onset is at about -0.32 V, whereas no photocurrent saturation was observed. The I-V measurements designated the deposited films as ohmic semiconductors.