Reflectins, a recently identified protein family that is enriched in aromatic and sulphur-containing amino acids, are used by certain cephalopods to manage and manipulate incident light in their environment. These proteins are the predominant constituent of nanoscaled photonic structures that function in static and adaptive colouration, extending visual performance and intraspecies communication. Our investigation into recombinantly expressed reflectin has revealed unanticipated self-assembling and behavioural properties, and we demonstrate that reflectin can be easily processed into thin films, photonic grating structures and fibres. Our findings represent a key step in our understanding of the property-function relationships of this unique family of reflective proteins.