Based on the unique fivefold equatorial coordination of UO₂²⁺, water-compatible pentadentate planar ligands, H₂saldian and its derivatives, were designed for the strong and selective capture of UO₂²⁺ in seawater. In the simulated seawater condition (0.5 M NaCl + 2.3 mM HCO₃^–/CO₃^2–, pH 8), saldian^2– shows the strongest complexation with UO₂²⁺ to form UO₂(saldian) (log β₁₁ = 28.05 ± 0.07), which is more than 10 order of magnitude greater than amidoxime-based or -inspired ligand systems most commonly employed for U capture from seawater. Good selectivity for UO₂²⁺ from other metal ions coexisting in seawater was also demonstrated.