The electronic structures of bis(pentafluorophenyl) zinc (I) and dichloro(N, N, N', N'-tetramethylethylenediamine) zinc(II) (II) have been investigated by HeI and HeII UV photoelectron spectroscopy (UPS) and DFT/ OVGF calculations. We discuss the properties of Zn-aryl and Zn-N bonds on the basis of spectroscopic evidence i.e. the nature of metal-ligand bonding. Our study is the first reported one on the photoelectron spectra of zinc-aryl complex. (C) 2008 Elsevier B. V. All rights reserved.