AbstractThe optical symmetry of many crystals is lower than would be expected from their external form and X‐ray diffraction data. Recently suchoptical anomalieshave been attributed to nonequilibrium structures resulting from kinetically controlled crystal growth. Impurities are incorporated to different extents at various surface sites that would otherwise have become symmetry‐related within the bulk crystal. After their discovery by Brewster in 1815, optically anomalous crystals were the subject of lively debate throughout the 19th century among some of the most distinguished contributors to the development of crystallography including Biot, Berzelius, Herschel, Mitscherlich, Frankenheim, Pasteur, Mallard, Klein, Groth, Wyrouboff, Barlow, Brauns, Rinne, Pockels, and Friedel. From a sea of wild speculation two conflicting postulates emerged: that the symmetric form resulted from accidental twinning of segments with lower symmetry, or that the optical peculiarities resulted from stress due to impurities or external perturbations. Neither postulate expresses the present view. Interest in this research waned at the turn of the century, and after 1917 no one pursued Tammann's alternative correct insight. The problem of anomalous double refraction attracted no attention for more than half a century until its recent solution. This review discusses both mineral and organic systems with particular emphasis on the phyllosilicate apophyllite and on 1,5‐dichloro‐2,3‐dinitrobenzene. These nonequilibrium structures relate to questions of crystal order, crystal growth, molecular recognition, and the design of new materials. The review provides a reminder of the enduring value of the polarizing microscope as a research tool in