In this perspective, we give an overview of several less explored structural and optical characterisation techniques useful for biomaterials. New insights into the structure of natural fibres such as spider silk can be gained with minimal sample preparation. Electromagnetic radiation (EMR) over a broad range of wavelengths (from X-ray to THz) provides information of the structure of the material at cor- respondingly different length scales (nm-to-mm). When the sample features, such as the alignment of certain fibres, cannot be characterised optically, polarisation analysis of the optical images can provide further information on feature alignment. The 3D complexity of biological samples necessitates that there be feature measure- ments and characterisation over a large range of length scales. We discuss the issue of characterising complex shapes by analysis of the link between the color and struc- ture of spider scales and silk. For example, it is shown that the green-blue color of a spider scale is dominated by the chitin slab’s Fabry-P ́erot type reflectivity rather than the surface nanostructure. The use of a chromaticity plot simplifies complex spectra and enables quantification of the apparent colors. All the experimental data presented herein are used to support the discussion on the structure-color link in the characterisation of materials.