By controlling the extent of hydrolysis during the self-assembly process of a zwitterionic-based ligand with uranyl cations, we observed a structural evolution from the neutral uranyl organic framework [(UO2)(2)(TTTPC)(OH)O(COOH)]center dot 1.5DMF center dot 7H(2)O (SCU-6) to the first cationic uranyl organic framework with the formula of [(UO2)(HTTTPC)(OH)]Br center dot 1.5DMF center dot 4H(2)O (SCU-7). The crystal structures of SCU-6 and SCU-7 are layers built with tetranuclear and dinuclear uranyl clusters, respectively. Exchangeable halide anions are present in the interlaminar spaces balancing the positive charge of layers in SCU-7. Therefore, SCU-7 is able to effectively remove perrhenate anions from aqueous solution. Meanwhile, the H2PO4--exchanged SCU-7 material exhibits a moderate proton conductivity of 8.70 X 10(-5) S cm(-1) at 50 degrees C and 90% relative humidity, representing nearly 80 times enhancement compared to the original material.