The mechanisms of photodegradation of binary iron- and uranium-citrate and ternary iron-uranium-citrate complexes were elucidated. Citric acid degradation products were identified by HPLC and GC, and the metal precipitates were identified by XRD and EXAFS. Photodegradation of a binuclear iron-citrate complex occurred as a result of two one-electron oxidations of citric acid with the formation of 3-oxoglutarate and two ferrous ions. The ferrous ions were reoxidized by a photo-Fenton reaction, resulting in the precipitation of iron as two-line ferrihydrite Fe(OH)3. The citric acid in the uranium-citrate complex underwent a two-electron oxidation to acetoacetate with the concomitant reduction of U(VI) to U(IV). The U(IV) was subsequently photooxidized in the presence of dioxygen with precipitation of uranium as the mineral schoepite (UO3 x 2H2O). A two-step electron reduction of two ferric ions to two ferrous ions wasthe primary mechanism for photodegradation of the ternary iron-uranium-citrate complex with oxidation of citric acid to 3-oxoglutarate; reduction of uranium was not observed. The iron precipitated as ferrihydrite and the uranyl ion as a uranyl hydroxide species. These results show the potential application of photochemical treatment of wastewater and decontamination solutions containing binary and ternary iron- and uranium-citrate complexes.