Display omitted ► Aqueous solutions of Fe(III)-oxalato complexes were photolyzed. ► The Fe(II) quantum yield decreases at Fe(III)<1×10−3M. ► Excitation energy influences Fe(II) quantum yield of dilute ferrioxalate solutions. ► 1:2 Fe(III)-oxalato complexes show higher quantum yields than 1:3 complexes. Iron(III)oxalato complexes do frequently occur in the environment, specifically in surface waters, in atmospheric waters (clouds, rain, fog) or in waste waters. Due to their high photo-reactivity and their absorption overlap with the actinic spectrum, Fe(III)oxalato complex photochemistry is widespread and of broad interest. Fe(III)oxalato complex photolysis in deaerated solutions using single excimer laser flash photolysis at 308 and 351nm and continuous Hg(Xe)-lamp irradiation at 313, 366 and 436nm was quantified via Fe(II) quantum yield measurements with phenanthroline complexometry and UV–vis detection. Measured Fe(II) quantum yields showed a dependence on initial Fe(III)ferrioxalate concentration and irradiation energy at below millimolar concentrations. Individual molar extinctions (in lmol−1cm−1) and individual quantum yields (Φ) were determined for initial Fe(III) concentrations of 4.85×10−4M for the 1:2 (FeOx2−) and 1:3 (FeOx33−) complexes applying a regression analysis for solutions containing variable ratios of 1:2 and 1:3 complexes: ɛ1:2, 308nm=2300±90, ɛ1:3, 308nm=2890±40, Φ1:3, 308nm=0.93±0.09; ɛ1:2, 351nm=1040±30, ɛ1:3, 351nm=1120±20, Φ1:3, 351nm=0.88±0.08; ɛ1:2, 313nm=2055±111, ɛ1:3, 313nm=2663±37, Φ1:3, 313nm=0.12±0.05; ɛ1:2, 366nm=753±357, ɛ1:3, 366nm=709±10, Φ1:2, 366nm=1.17±1.46, Φ1:3, 366nm=0.91±0.09; ɛ1:2, 436nm=55±9, ɛ1:3, 436nm=22±2, Φ1:2, 436nm=1.40±0.40, Φ1:3, 436nm=1.00±0.20. Individual quantum yields for the 1:2 complex could only be determined for the excitation wavelengths 366 and 436nm due to non-linearity of the data for 308, 351 and 313nm. The non-linearity is ascribed to complicated interactions of secondary reactions involving Fe(III)oxalato educt-complexes, carboxyl radicals and Fe(II)-radical complexes. The 1:2 complex has generally a higher quantum yield compared to the 1:3 complex at all considered wavelengths.