The marked temperature‐dependent uptake of a commercial disperse dye on poly(ethylene terephthalate) fabric achieved during an aqueous high temperature dyeing process is the likely amalgamation of at least two separate, but intrinsically inter‐related, thermally activated processes, namely, poly(ethylene terephthalate) structural relaxations, as articulated in terms of polymer chain segmental mobility and available free volume, in which glass transition adopts a principal role, as well as disperse dye aqueous solubility. Both polymer relaxation times and disperse dye solubility therefore assume crucially important roles in the mechanism of adsorption of disperse dyes on poly(ethylene terephthalate) fibres.