The solution synthesis of large single crystals of octahedron-like anatase TiO2 is reported, although this novel result is unexpected in the light of reported theoretical calculations. Moreover, systematic control of the crystal growth of rutile nanopins on the microanatase octahedron single crystal results in a nano-micro chestnut-like TiO2 structure. The control of the formation of rutile nanopins on the large single crystals of anatase in the same solution is an interesting and useful technique, based on thermodynamics and surface chemistry.