Our high-level ab initio calculations show that the ZnCl 2+ ground state of 2Π symmetry is metastable with a bond length of 2.242Å, an effective dissociation energy of 1.66eV, and an adiabatic double ionization energy of ZnCl of 26.11eV. Potential energy curves for 18 Λ+S states and ten Ω states of ZnCl 2+ are presented as well as the associated spectroscopic constants. Tunneling lifetimes, spin–orbit induced predissociation lifetimes and radiative lifetimes for the vibrational levels in the low-lying electronic states of ZnCl 2+ are determined and the metastability of the dication is discussed.