Single crystals of B12 TiO20 are grown from solutions containing an excess of Bi2O3 by the TSSG (“top‐seeded solution growth”) technique. Doping with iron, manganese, aluminium, and chromium is performed by adding the oxides to the melt. Measurements of dielectric constant, refractive indices, optical activity, absorption, light‐induced absorption, and dark conductivity are performed.