Metastable fragmentation of neon dimer ions has been investigated by measuring and analyzing high resolution kinetic energy release distributions. Data were obtained by a modified MIKE (mass-analyzed ion kinetic energy) scan technique. Due to the high energy resolution it was possible to distinguish two different reaction mechanisms in the micros time regime which produce Ne+ ions with different kinetic energy distributions. Theoretical studies based on ab initio calculations of potential energy curves allowed the assignment of the reactions to specific electronic transitions in the excited Ne2+ ion. The unusual bimodal kinetic energy release distribution arises from competition between radiative and non radiative decay of the long-lived Ne2+ II(1/2)u state.