The tetrathionate anion has the potential to oxidise thiols specifically to disulphides; this property has been investigated in this paper from the point of view of using tetrathionate as an anti‐setting agent in wool dyebaths. It was found that at pH 3 the addition of tetrathionate actually made the degree of permanent set greater than in its absence; however at pH 5 and pH 7 significant anti‐setting benefits were achieved. The reason for the apparently contradictory result at pH 3 was found to be the substantivity and subsequent reactivity of thiosulphate anion for wool – this anion is a product of the reduction of tetrathionate by wool cysteinyl thiol residues.