To explore the innovative uranyl(V) complexes by deeply understanding their coordination stability, relativistic density functional theory calculations have been performed to investigate the experimentally reported [(py)(R2AlOUVO)(py)(H2L)] [R = Me (1), iBu (2)] and [{(py)3MOUVO}(py)(H2L)] [M = Li (3), Na (4), K (5)] and their uranyl(VI) counterparts. Structural and topological analyses along with transformation-reaction energies and redox potentials were systematically studied. Geometrical and quantum theory of atoms in molecules analyses implied a linear U-Oexo-M feature in 1-3 and a bent one in 4 and 5. The calculated free energies (ΔrG) of reactions transforming 1/2 into 3/4/5 confirmed a higher stability of the latter ones, which were further corroborated by their reduction potentials (E0). The E0 value of 5 versus uranyl(VI) is close to its experimental value, particularly in solvation with spin-orbit coupling. The highest occupied and lowest unoccupied molecular orbitals of uranyl(V) and uranyl(VI) have predominant U(5fδ) character. Compared to mononuclear uranyl(VI), the coordination of aluminum and alkali metals to uranyl exo-oxo significantly contributes to the stabilization of uranyl(V) by altering the E0 value from -1.59 to -0.85, -0.91, -1.33, -1.50, and -1.46 V, respectively. The calculation results show a more positive E0 than that of the precursor 6VI/6 without exo-oxo coordination. The calculated E0 values of 3-5 are certainly more negative than those of 1 and 2. The alkali metals were found to activate U═O bonds more easily/readily than aluminum by coordination to the exo-oxo atom. In brief, the uranyl exo-oxo cation-cation-interaction enhanced the reduction ability from its uranyl(VI) analogue and raised the stability of the UV center.