We show that the transformation of benzene into phenol is a more selective probe for the hydroxyl radical than the transformation of nitrobenzene or the generation of 4-hydroxybenzoic acid from benzoic acid. The benzene to phenol system showed adequate performance as a probe upon irradiation of lake water samples and humic acids. We show that the use of nitrobenzene and benzoic acid as hydroxyl probes should be avoided because of poor selectivity. Moreover, all the tested probe molecules underwent important interference by irradiated antraquinone-2-sulphonate, and considerably overestimated the formation of the hydroxyl radicals.