We studied the ligand-enhanced sorption of uranyl ions (1-12 μM) on α-alumina colloids suspended in (and pre-equilibrated with) solutions at various concentrations of phosphate ions (P(T) = 0-900 μM). A highly sensitive technique, time resolved laser-induced fluorescence spectroscopy (TRLFS), was used to examine the chemical speciation of uranyl sorbed at trace concentrations (0.4-4 μmol U·g⁻¹). The suspensions with P(T) ≥ 100 μM exhibited high uranyl adsorption, and a very high intensity of fluorescence that increased with the sorbed amounts of phosphate and uranyl. These samples exhibited similar spectral and temporal characteristics of fluorescence emission, evidencing a uniform speciation pattern and a single coordination environment for sorbed U, despite large variation in parameters such as aqueous uranyl speciation, U loading, and extent of coverage of alumina by secondary Al phosphates precipitating on the surface. The results pointed formation of surface precipitates of uranyl phosphates, which are characterized by high quantum yield, peak maxima at positions similar to those of U(VI) phosphate minerals and four lifetimes indicating distortions, in-homogeneities or varying number of water molecules in the lattice. The findings have major implications for our understanding of the mechanisms of immobilization of U at trace levels on surfaces of oxides submitted to phosphated solutions in soils with low pH.