A kinetic-based rationale to assess the role of each excited species in thermodynamically favoured photocatalytic processes at different pollutant concentrations, has been developed and illustrated with new experimental data. Specifically, 2,4,6-triphenylthiapyrylium (TPTP+) salt has been chosen as a representative organic compound capable to act as photocatalyst, and the possible involvement of its excited states in the photodegradation of pollutants commonly found in aqueous ecosystems has been investigated using five chemicals, namely acetaminophen, acetamiprid, caffeine, clofibric acid and carbamazepine. First, steady-state photolysis has been carried out under simulated solar irradiation in the presence of TPTP+, and second, photophysical measurements (fluorescence and laser flash photolysis) have been performed in order to obtain reliable fast kinetic data. Thermodynamic considerations allow ruling out energy transfer processes, while the kinetic results are in good agreement with an electron transfer to the triplet excited state of TPTP+. Hence, the higher the intersystem crossing quantum yield the better. Although quenching of the singlet excited state is also observed, the contribution of this reactive species is only minor, due to its shorter lifetime. In general, the efficiency of a photocatalyst should be enhanced at higher pollutant concentrations, at which the intrinsic decay of the triplet excited state is minimized. (C) 2016 Elsevier B.V. All rights reserved.