Both pigmentary and structural colours share many common elements of their feather anatomy, i.e. keratin, air and melanin packed in the melanosomes, despite utilizing different mechanisms of the colour production. This means that evolutionary transitions between pigmentary and structural colours can be achieved through a simple adjustment of these elements. Recently, an evolutionary hypothesis for the transition between pigmentary grey, through slate and finally to structural blue colour has been proposed and confirmed in the clade Tanagers on a macroevolutionary level. Here, we investigate mechanistic basis of this evolutionary pathway. By using SAXS (small-angle X-ray scattering) we have quantified important elements of spongy layer in medullary cells that is crucial for colour production by coherent scattering of light wavelengths. We have quantified five elements of the spongy layer: nanostructure complexity, average hard block thickness, average soft block thickness, filling fraction and Iovalue. We report that across different categories of feather colour, i.e. blue, slate and grey, nanostructure complexity, filling fraction and Iovalue explained variation in the chromatic component of the colour (between the three colour categories). Chromatic variation within the colour category was explained by filling fraction in the case of slate colour and by nanostructure complexity and average hard block thickness in the case of blue colour. We propose that variation in different elements or combination of elements of the spongy nanostructure has been utilised in feather colour evolution, both within and between colour categories, to overcome developmental constraints imposed by self-assembly processes.