This study of aqueous metal speciation is an advanced combination of theoretical and experimental methods. Continuous wave (CW) and time-resolved laser-induced fluorescence spectroscopy (TRLFS) data of uranyl(VI) hydrolysis were analyzed using parallel factor analysis (PARAFAC). Distribution patterns of five major species were thereby derived under a fixed uranyl concentration (10-5 M) over a wide pH range from 2 to 11. UV (180 nm to 370 nm) excitation spectra were extracted for individual species. Time-dependent density functional theory (TD-DFT) calculations revealed ligand excitation (water, hydroxo, oxo) in this region and ligand-to-metal charge transfer (LMCT) responsible for luminescence. Thus excitation in the UV region is extreme ligand sensitive and specific. Combining findings from PARAFAC and DFT the [UO 2 (H 2 O) 5 ] 2+ cation (aquo complex 1 : 0) and four hydroxo complexes (1 : 1, 3 : 5, 3 : 7 and 1 : 3) were identified. The methodological concept used here is applicable to luminescent metals in general and thus enables acquisition of refined structural and thermodynamical data of lanthanide and actinide complexation.