Irradiation of the complex or the chromate(VI)-oxalate mixture, or the ternary system composed of Cr(III), Cr(VI) and oxalate, leads to chromium photoreductions in consequence of the ligand to metal charge transfer (LMCT) excitations induced by artificial solar radiation. In the case of the Cr(III) complex, the photoreduction involves the innersphere electron transfer leading to the formation of the Cr(II) species and the radicals. On reacting with molecular oxygen, Cr(II) is oxidised to Cr(III) catalysing thereby the oxalate substitution reaction. Moreover, under specific conditions, Cr(II) can be also oxidised to Cr(VI). Chromate(VI) is not photoreducible, but in the presence of oxalate, or other sacrificial electron donor, the outersphere photoinduced electron transfer (PET) produces Cr(V) species and the radicals. This initiates a series of thermal reactions leading to the formation of Cr(III) and oxidized oxalate (CO2). In the system composed of and chromate(VI), the acidic medium and anoxic conditions favour the Cr(VI) photoreduction, whereas alkaline oxygenated solutions assist the Cr(VI) photoproduction. When an approximately neutral solution equilibrated with the ambient air is irradiated intermittently, Cr(VI) is consumed and/or produced, accordingly to the time sequence of exposure and dark periods. The oscillations of Cr(VI) concentrations are accompanied by continuous oxidation of oxalate, playing the role of the sacrificial electron donor. The effects of solution pH, molecular oxygen, concentrations of reagents and cations on the reaction rates were investigated. The results of this paper revealed that the Cr(III)/Cr(VI) system under environmental conditions behaves as the photocatalytic one catalysing the oxidation of oxalate or other organic matter by molecular oxygen, contributing thereby to the abatement of pollution.