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[Display omitted] • TiO 2 -rGO at the solar assisted photodegradation of complex mixing of pesticides. • Best photocatalytic performances with oxygen, regardless of the water matrix. • H 2 O 2 has not improved the final photocatalytic efficiency in any case. • P25-rGO promoted the photo-oxidation of the complex pesticides mix studied. • HBK-rGO presented excellent solar photoefficiency with 200 μg L-1 of pesticides. New titania-reduced graphene oxide (TiO 2 -rGO) nanocomposites have been studied to assess their application in the solar assisted photodegradation of a complex mixing of pesticides (pyrimethanil, isoproturon, alachlor and methomyl) at solar pilot plant, opening the opportunity to extend the use of these hybrid photocatalysts to complex wastewater effluents. TiO 2 -rGO nanocomposites were prepared by hydrothermal method from two commercial TiO 2 , Hombikat UV-100 (HBK) and Aeroxide® P25 (P25). The effect of two different water matrices (simulated and natural) on TiO 2 -rGO solar photoefficiency with two pesticides concentrations (5 mg·L−1 and 200 μg·L−1), and the additional use of an electron scavenging as oxidant agent, such as hydrogen peroxide in a comparison with oxygen from air, has been studied in compound parabolic collectors (CPC) photoreactors. Best photocatalytic performances were always found with oxygen over both TiO 2 -rGO nanocomposites, regardless of the water matrix employed. The use of H 2 O 2 as oxidant agent has not improved the final photocatalytic efficiency in any case. The generation of secondary highly reactive species in the reaction media from reaction of SO 4 ●- /HO radicals, and the more negatively surface charge with low S BET of P25-rGO nanocomposite, besides its lower hydrodynamic size with lower particle aggregation in the reaction conditions, have been responsible to promote the photo-oxidation of the complex pesticides mix studied. Finally, HBK TiO 2 -reduced graphene oxide (HBK-rGO) nanocomposite has presented excellent solar photoefficiency in the photodegradation of 200 μg·L−1 of each pesticide with the oxygen form air, especially under natural water matrix, because of its large negatively charge surface area where probably recombination of electrons and holes is prevented. [ABSTRACT FROM AUTHOR]