The role of transition metal complexes is overviewed for the iron, copper and chromium compounds, for which photoreactivity is of crucial environmental importance. Attention is paid to these complex systems, in which metal centres are photoreduced by organic matter under solar irradiation and re-oxidized by molecular oxygen, i.e. to the systems, that play a part in the environmental photocatalysis. The photoreduction is accompanied by simultaneous oxidation of organic matter, which plays a role of ligand and/or sacrificial electron donor. Under favourable conditions a complete photodegradation of the organic pollutants can be achieved. The general mechanisms are analysed and examples of different photocatalytic behaviours are presented in some details. The systems are more sophisticated due to concurrent generation of active oxygen species. such as the O-2(.-), HO2.. OH., H2O2, and HO2-, which are involved in the redox reactions of the photocatalytic cycling and influence the pollutant degradation. Beside the monometallic cycles, the mixed metal systems can function in nature. The cooperation between the photocatalytic cycles of two metals can abate diverse environmental pollutants, but their efficiency can be either higher or lower in comparison with that of the sum of single cycles. (C) 2004 Elsevier B.V. All rights reserved.