Variation of iron species in the UV-irradiated aqueous solution was examined in the presence of various dissolved organic matter (DOM). Under the irradiation at constant light intensity, a regular oscillation in the ratio of Fe(II) to total iron, Fe(II)/Fe(t), was observed when DOM was periodically added into the solution. In each cycle, the Fe(II)/Fe(t) ratio increased initially and then decreased with concomitant degradation of DOM. The Fe(II)/Fe(t) ratio approached a constant value after the DOM was completely mineralized. The period and amplitude of the oscillation were dependent on DOM structure and its initial concentration, but the ultimate photosteady state was not affected by DOM. It was revealed that both DOM and photoreactive Fe(III) species were indispensable for the fluctuation in Fe(II)/Fe(t) ratio. The ultimate photosteady state originated from the equilibrium between Fe(III) photoreduction and aerobic Fe(II) photooxidation induced simultaneously by UV irradiation. It was the DOM that disturbed these two opposite processes, leading to the oscillation in Fe(II)/ Fe(t) ratio under UV irradiation.