Three N,N-substituted pyridine 2-carboxamide ligands, C5H4NCONRR′ (where, R, R′ = iC3H7 (L1); R, R′ = iC4H9 (L2); and R = H, R′ = tC4H9 (L3), as well as their coordination complexes (1–3) of uranyl nitrate have been synthesized. All the ligands and their corresponding complexes were characterized by CHN elemental analysis, infrared (FTIR) and NMR spectroscopy. The crystal structure of the complex 1 shows that the central uranium atom occupies a distorted hexagonal bipyramidal geometry, where the four oxygen atoms of the bidentate nitrate ligands with the oxygen and nitrogen atoms of the ligand L1 form the hexagonal plane and two axial oxygen atoms of uranyl occupy the trans axial position. Here, the ligand acts as a bidentate chelating ligand. The preliminary structural analysis of the complex 3 also indicates similar kind of structure as that of the complex 1. Quantum mechanical calculation at DFT level is supportive with the solid state structure obtained from X-ray crystallographic analysis.