This paper reports the development of novel surface parameters which can be used to characterise the scale structure of wool fibres obtained from different breeds. Scanning Electron Microscopy and subsequent image analysis technique were used to study wool fibres from Leicester, Dartmoor, Ryeland and Herdwick breeds of sheep. Novel scale parameters related to wool fibre's effective chemical diffusion pathway were developed. Namely, the total scale perimeter per 100 µm fibre length and scale perimeter index, which is the total scale perimeter per 100 µm length divided by the fibre diameter. Wool fibres obtained from different breeds showed significant differences in their scale pattern with the change in fibre diameter. The scale perimeter per 100 µm length increased with the fibre diameter and showed a polynomial correlation. It was also demonstrated that an increase in the diameter of the wool fibre resulted in an increase in the apparent dye diffusion coefficient, which contrasts the established theory that finer fibres are associated with a higher dyeing rate. The increase in effective diffusion pathway (total scale perimeter per 100 µm) for the wool fibres (among different breeds) resulted in a higher dye diffusion rate at the initial phase of dyeing (liquor to surface).