Previously published kinetic‐derived data reported for the temperature‐dependent diffusional behaviour of two direct dyes and a reactive dye within both cellophane and cotton substrates, in the presence of both a constant amount and varying amounts of added inorganic electrolyte, and over a diverse range of dyeing temperatures, were re‐evaluated using the Williams–Landel–Ferry equation. The experimentally observed diffusivity of the various anionic dyes within both types of cellulosic material and the structural relaxation times of the respective, water‐plasticised, cellulose I and cellulose II macromolecules, were shown to be intrinsically related, thermally regulated phenomena. The plasticisation model of dye diffusion seems to offer a plausible explanation of the temperature‐dependent diffusional behaviour of direct dyes and reactive dyes within cellulosic fibre/polymers in the presence of added inorganic electrolyte.