A theoretical study on the decomposition pathways of N-7(+) and N-7(-) clusters with low spin has been carried out on the basis of ab initio molecular orbital theory and density functional methods. Transition states of dissociation processes were found and characterized on the MP2/6-31(+)G(d) and B3LYP/6-31(+)G(d) potential energy surfaces (PES). Relative energies were further calculated using a basis set extrapolation similar to the G2(MP2) method for the MP2/6-31(+)G(d) optimized geometries. B3LYP/6-311+G(3df, 2p) single-point energy corrections were performed using the B3LYP/6-31(+)G(d) geometries. The present study shows that the elimination of two N-2 in the open-chain anion N-7(-) (C-2) is a concerted process, whereas in the open-chain cation N-7(+) (C-2nu), it is stepwise due to the existence of stable linear N-5(+). The decomposition pathway of the cyclic anion N-7(-) (C-s) was also investigated at the above levels. The computed results suggest that the N-7 ions do not seem to be stable enough as a metastable species in a practical sense.