A WO-organic (LMO = layered metal oxide) hybrid precursor route has been developed to synthesize rectangular (WO3)(n) structures. In the present work, regular rectangular orthorhombic (WO3)(n) has been fabricated by a thermal decomposition of the as-synthesized rectangular [WO3(bPY)(0.5)](n) (bpy = 4,4'-bipyridine) precursor, which is formed by a process of intercalation, coordination, and self-assembly using the hydrothermal treatment of (WO3)(n) and 4,4'-bipyridine. The precursor and final products were characterized by field-emission scanning electron microscopy, transmission electron microscopy, electron-induced X-ray fluorescence analysis, X-ray diffraction analysis, derivative thermogravimetry analysis, and thermog ravi metric analysis.