High-resolution Cl (2p) photoelectron spectra Of Cl-2 are reported and their complex structure is analyzed in detail, taking into account molecular field (NIF), spin-orbit (SO) and parity splitting. High-level ab initio calculations were performed to provide reliable values for spectroscopic parameters. Accurate data analysis enabled us to determine the value of molecular-field splitting of 86 7 meV, and values of 92 5, 79 11 and 105 12 meV for the lifetime line widths of the (2)Pi(1/2), (2)Sigma(+)(1/2) and (2)Pi(3/2) states, respectively. The gerade-ungerade splitting of less than 5 meV is obtained from the calculations. (c) 2006 Elsevier B.V. All rights reserved.