The structural studies of potassium hexatitanates prepared under both hydrothermal and solid state conditions were carried out. Fourier Transform Infra-red spectroscopy (FTIR) results revealed that potassium hexatitanate structure consisted of TiO6 octahedral units irrespective of the preparative conditions and particle size. X-ray diffraction (XRD) results showed that the only potassium hexatitanate phase was detectable and the structure is of the Wadsley-type consisting of chains of Ti-O octahedral sharing edges with tunnels in which the potassium ions are located. From scanning electron microscopy (SEM) results, the different preparative conditions resulted in different particle sizes and morphologies of the potassium hexatitanate formed.