Two-dimensional multistate potential energy surfaces along N–NO bond length and N–N–O bond angle of N₂O⁺ in the A²Σ⁺ and B²Π states were calculated at the CASPT2/cc-pVQZ level. In comparison to the known decomposition mechanisms in linear structure, a new N–NO bond fission pathway was proposed in bent geometry for the A²Aʹ(A²Σ⁺) state with a lower barrier, leading to rotationally excited NO⁺(X¹Σ⁺) and N(²D) fragments. Likewise, the respective contributions of the Aʹ and A^″ components split from the B²Π state were clarified. Considering avoided crossing and the coupling of spin states, ro-vibrational distributions of the NO⁺ fragment ion observed in experiments are elucidated.