Unacceptably high uranium concentrations in decentralized and remote potable groundwater resources, especially those of high hardness (e.g., high Ca2+, Mg2+, and CO32- concentrations), are a common worldwide problem. The complexation of alkali earth metals, carbonate, and uranium(VI) results in the formation of thermodynamically stable ternary aqueous species that are predominantly neutrally charged (e.g., Ca2(UO2)(CO3)30). The removal of the uncharged (nonadsorbing) complexes is a problematic issue for many water treatment technologies. As such, we have evaluated the efficacy of a recently developed electrochemical technology, termed flow-electrode capacitive deionization (FCDI), to treat a synthetic groundwater, the composition of which is comparable to groundwater resources in the Northern Territory, Australia (and elsewhere worldwide). Theoretical calculations and time-resolved laser fluorescence spectroscopy analyses confirmed that Ca2(UO2)(CO3)30 was the primary aqueous species followed by Ca(UO2)(CO3)32- (at circumneutral pH values). Results under different operating conditions demonstrated that FCDI is versatile in reducing uranium concentrations to <10 μg L-1 with low electrical consumption (e.g., ∼0.1 kWh m-3). It is concluded that the capability of FCDI to remove uranium under these common conditions depends on the dissociation kinetics of the Ca2(UO2)(CO3)30 complex in the electrical field. The subsequent formation of the negatively charged Ca(UO2)(CO3)32- species results in the efficient transport of uranium across the anion exchange membrane followed by immobilization on the positively charged flow (anode) electrode.