The aim of this work is to characterize the complexation ability of F-, BF4-, PF6-, and Tf2N- toward uranyl ions in aqueous solution. These anions were chosen as they represent the anionic part of the most studied room-temperature ionic liquids. Time-resolved emission spectroscopy and X-ray absorption spectroscopy were used to retrieve structural data on the complexes formed. The results obtained were compared with computational data. Tf2N- does not complex uranyl, even at high concentration. Other fluorinated acids form inner-sphere complexes with U(VI), in a monodentate fashion in the case of BF4- and PF6-.