Identification of sorption species of uranium (U) on clay minerals by spectroscopic techniques would consolidate the reliability of predicted sorption models. However, it is still challenging, especially, under complex environmental conditions, where the surface loading is low, and quenching elements for spectroscopic analyses hamper the application. In light of this, the sorption of U(VI) on illite at different pH and dissolved inorganic carbon (DIC) levels was investigated by using batch experiments, surface complexation modeling, and cryogenic time -resolved laser fluorescence spectroscopy (cryo-TRLFS) combined with parallel factor analysis (PARAFAC). The inhibiting effect of DIC on U(VI) sorption was revealed by the macroscopic batch experimental results. However, there was still sorption of U(VI) on illite even at a high DIC (19 mM), validating certain retention capacities of illitic clay minerals for U(VI) even from pore waters with high DIC. An updated 2 -site protolysis non -electrostatic surface complexation and cation exchange model considering the formation of two uranylcarbonate sorption complexes was able to reproduce the experimental results well. Based on the PARAFAC analysis on the cryo-TRLFS spectra, there was clear correspondence in the variation trend of the derived components with the sorption species from the modeling results, validating the formation of ternary uranyl-carbonate sorption species. The results imply that ternary uranyl-carbonate sorption species need particular consideration in the modeling of U(VI) sorption on clay minerals at high DIC levels. Identifying the sorption species adds more credibility to the predictive sorption model, which provides more confidence in the safety assessment of deep geological disposal. In addition, these results help better understand the fate of uranium during transport in geological disposal -related environments.