A new 3-fold interpenetrated uranyl organic framework, UO2(bdc)(dmpi), was hydrothermally synthesized using 1,4-benzenedicarboxylic acid (H2bdc) and 1-(4-(1H-imidazol-1-yl)-2,5-dimethylphenyl)-1H-imidazole (dmpi). This framework, which was determined by synchrotron radiation X-ray, exhibited a new 3-fold interpenetrated (2,4)-connected topology with the Schläfli symbol of (12(6))(12)2. Additionally, large incurvation happened to the bond angle of [O=U=O](2+), which was always arranged in a rigorous line. Computational results based on density functional theory (DFT) indicated that the bent geometry of uranyl in UO2(bdc)(dmpi) was mainly due to the higher charge populations in the valence 6d shells of uranium, rendered by the electronegative imidazoles.