Single crystal growth and domain structure of Rh:Barium titanate (BaTiO3) have been investigated. Rh doping in BaTiO3 is effective for the growth of bulk crystals without twin formation. Atomic force microscope (AFM) and optical microscope studies reveal the formation 180°and 90°domains on the grown crystals. It has been observed that the complex 180°domain structure with typical size of around 20 μm exists in the c-domain of {0 0 1} face of Rh doped BaTiO3 crystals. © 2005 Elsevier B.V. All rights reserved.