Hierarchical durian‐shaped dodecahedrons of rutile have been synthesized hydrothermally from titanium n‐butoxide (TNB) in oxalic acid. The products are characterized by powder X‐ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and selected‐area electron diffraction (SAED) and the hierarchical architectures of these dodecahedrons have been addressed. It is suggested that the growth of the hierarchical rutile architectures is directly from a precursor, titanium oxide oxalate hydroxide hydrate [Ti2O2(C2O4)(OH)2·H2O, briefly denoted as TOOHH], which can be formed at an earlier stage during hydrothermal synthesis, typically at lower reaction temperature. The production of the novel hierarchical nanostructure is attributed to epitaxial growth along some specific directions and the chemical etching and growth is due to similarities of corner‐sharing TiO2 octahedrons between rutile and TOOHH.