Artificial opals are self-assembled colloidal crystals, which consist of a cubic dense packing (fcc) of hard (not film-forming) colloids with diameters ranging from 200 to 900 nm. Because of their periodic nanostructure the assemblies are able to reflect light that matches their periodicity, i.e., UV- to IR-radiation depending on the size of the colloids. Thus, they present a subgroup of ‘photonic crystals’. While, originally, the chemistry inside the colloids and the resulting opals was of minor significance, nowadays the chemical variation of opals is becoming more and more important for the preparation of functional and patterned opals. The search for functional opals is, therefore, especially focused on four topics: I) coloring agents, II) incorporation of fluorescent materials, III) replication, and IV) the controlled incorporation of defects.