Maya Blue, an ancient nanostructured organic–inorganic hybrid material resulting from the attachment of indigo, a natural dye, to a phyllosilicate clay, palygorskite, has received considerable attention of late. Despite intensive research, several aspects remain unsolved, in particular the nature of the indigo–palygorskite association. Recent results suggest that the Maya Blue pigment is a complex system in which different topological isomers of various indigoid molecules attached to the palygorskite matrix coexist.