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In this paper, the effect of β‐cyclodextrin as an additive in the dyeing of polyester with disperse dyes, as a substitute for a commercial surfactant commonly used, was explored with the aim of reducing the environmental impact of the exhausted baths. Using a chemometric approach, a small group of dyes was selected as a ‘training set’ to be representative of a larger series of dyes with a similar structure. The selected dyes were synthesised and applied to the dyeing of polyester fibres under various conditions. The technological properties of the dyed samples were measured. The results showed that β‐cyclodextrin can satisfactorarily be used as an additive in dyebaths for polyester without the addition of other auxiliaries, with a positive environmental impact. Solubility isotherms evidenced dye–β‐cyclodextrin interactions. The formation of inclusion complexes did not produce negative effects on the dyeing performance. Light fastness values were modelled as a function of the structure by the chemometric partial least squares method and the established model was used to predict the fastness of dyes of analogous structure, not yet explored.

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