Zinc oxide nanoplatelets have been successfully grown on Si(l00) by a catalyst-free Chemical Vapor Deposition (CVD) route starting from a second-generation Zn(II) molecular precursor, Zn(hfa)2⋅TMEDA (Hhfa=1,1,1,5,5,5-hexafluoro-2,4-pentanedione; TMEDA=N,N,N',N'- tetramethylethylenediamine). The syntheses were performed under a nitrogen+wet oxygen atmosphere and the best results were obtained at deposition temperatures of 350 and 400 °C. The obtained samples were thoroughly characterized by several techniques, namely Glancing-Incidence X-ray Diffraction (GIXRD), Atomic Force Microscopy (AFM), Field Emission-Scanning Electron Microscopy (FE-SEM), Energy Dispersive X-ray Spectroscopy (EDXS), X-ray Photoelectron (XPS) and X-ray Excited Auger Electron (XE-AES) Spectroscopies. Finally, the photocatalytic performances of ZnO nanoplatelets in the decomposition of the azo-dye Orange II were also evaluated. The present contribution is specifically dedicated to the XPS and XE-AES characterization of a representative ZnO nanoplatelet sample deposited at 350 °C. Beside the wide scan spectrum, detailed spectra for the Zn 2p3/2, Zn 3p, Zn LMM, O 1s, and C 1s are also presented. The obtained results evidenced the formation of pure zinc oxide systems under the adopted synthetic conditions.