The redox flow battery using uranium as the negative and the positive active materials in polar aprotic solvents was proposed. In order to establish the guiding principle for the uranium compounds as the active materials, the investigation of uranium β-diketonate complexes was conducted on (i) the solubility of active materials, (ii) the electrode reaction of U(VI) and U(IV) β-diketonate complexes and (iii) the estimation of the open circuit voltage of the battery. The solubilities of higher than 0.8 mol dm−3 of U(VI) complexes and higher than 0.4 mol dm−3 of a U(IV) complex were obtained in the solvents. The electrode reactions of U(pta)4, UO2(dpm)2, UO2(fod)2 and UO2(pta)2 were first studied and the redox potentials of uranium β-diketonates were thermodynamically discussed. The open circuit voltage is estimated more than 1 V by using Hacac or Hdpm. The larger open circuit voltage is expected when a ligand with the larger basicity is used.