We report a joint photoelectron spectroscopic and relativistic quantum chemistry study on gaseous NUO2-. The electron affinity (EA) of the neutral NUO2 molecule is reported for the first time with a value of 2.602(28) eV. The U-O and U-N stretching vibrational modes for the ground state and the first excited state are observed for NUO2. The geometric and electronic structures of both the anions and the corresponding neutrals are investigated by relativistic quantum chemistry calculations to interpret the photoelectron spectra and to provide insights into the nature of the chemical bonding. Both the ground state of the anion and neutral are calculated to be planar structures with C2v symmetry. Unlike the "T"-shape structure of UO3 which has a quasi-linear O-U-O angle, both the ground-state geometries of the anion and neutral have O-U-O bond angles of around 90°. The significant contraction of the O-U-O bond angle indicates the strong interaction between the U and N atoms compared with the "additional" oxygen in UO3. The chemical bonding calculation indicates that multiple bonding of U(VI) can occur in NUO2- and NUO2, and the UVI-N bond is significantly more covalent than the U-O bond. The current experimental and theoretical results reveal the difference between the U-N and U-O bond in the unified molecular system, and expand our understanding of the bonding capacities of actinide elements with the nitrogen atom.