Abstract : The first coordination sphere of the uranyl cation in room-temperature ionic liquids (ILs) results from the competition between its initially bound counterions, the IL anions, and other anions (e.g., present as impurities or added to the solution). We present a joined spectroscopic (UV-visible and extended X-ray absorption fine structure)-simulation study of the coordination of uranyl initially introduced either as UO2X2 salts (X- = nitrate NO3-, triflate TfO-, perchlorate ClO4-) or as UO2(SO4) in a series of imidazolium-based ILs (C(4)mimA, A(-) = PF6-, Tf2N-, BF4- and C(4)mim = 1-methyl-3-butyl-imidazolium) as well as in the Me3NBuTf2N IL. The solubility and dissociation of the uranyl salts are found to depend on the nature of X- and A(-). The addition of Cl- anions promotes the solubilization of the nitrate and triflate salts in the C(4)mimPF(6) and the C(4)mimBF(4) ILs via the formation of chloro complexes, also formed with other salts. The first coordination sphere of uranyl is further investigated by molecular dynamics (MD) simulations on associated versus dissociated forms of UO2X2 salts in C(4)mimA ILs as a function of A(-) and X- anions. Furthermore, the comparison of UO2Cl42-, 2 X- complexes with dissociated X- anions, to the UO2X2, 4 Cl- complexes with dissociated chlorides, shows that the former is more stable. The case of fluoro complexes is also considered, as a possible result of fluorinated IL anion's degradation, showing that UO2F42- should be most stable in solution. In all cases, uranyl is found to be solvated as formally anionic UO(2)X(n)A(m)Cl(p)(2-n-m-p) complexes, embedded in a cage of stabilizing IL imidazolium or ammonium cations.