The single phase layered perovskite-type niobate KCa2Nb3O10 was obtained by a solid state reaction of the starting materials (K2CO3, CaCO3 and Nb2O5) at 1,200 °C. Then the H(+)-exchanged form (HCa2Nb3O10) was successfully exfoliated into colloidal porous single layers on the intercalating action of tetra(butyl)ammonium ion. The various characterization techniques such as X-ray diffraction (XRD), field-emission scanning electron microscopy, N2 absorption-desorption and diffuse reflectance UV-visible spectrometry gave important information on the unusual structural features of the perovskite-related niobate nanosheets. XRD analysis of the exfoliated nanosheets showed a unique profile with wide peaks that represented individual molecular aspects of the nanosheets. The Brunauer-Emmett-Teller isotherm of the exfoliated coiled nanosheets showed a sharp increase in the surface area by a factor of >30 in comparison to parent layered material, which is due to the exfoliation and restacking process. The nanosheets in this study were also found to act as a semiconductor with a wide band gap that is due to the quantum size effect.