Abstract: Density functional theory calculations have been performed on a series of uranyl-ligands to investigate. The computational findings are in good agreement with available data from literature, with average error in bond length below 0.006 nm, which verifies rationality of calculation method and parameter settings. The structural, electronic, and thermochemical properties of uranyl complexing with acethydrazide, acetohydroxamic acid, N-hydroxyacetamidine, and methyl amidoxime were studied. Results show that compared with other ligands, methyl amidoxime in η₂ configuration complexing with uranyl displays best selectivity. Through caculation of molecular orbitals, —C＝N—O exists p-π conjugation effect which enhances coordination properties. From the point of substituent inductive effect, ligand structure was designed.