Thermally stable lamellar crystalline zirconia (TSLCZ) was synthesized using sodium dodecyl sulphonate (SDS, C-12 H25SO3Na) as supermolecular template via a novel 'reflux-hydrothermal' hybrid method (R-HT). ZrOCl2 and NaOH were used as Zr source and precipitant, respectively. The products were investigated by X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FE-SEM) and Transmission Electron Microscopy (TEM). Results show that TSLCZ exhibits ordered lamellar structure, multilayers morphology and good hierarchical thermostabilities from crystal to nanostructure to microstructure at 500 degrees C. This novel R-HT route ensures the controllable nucleation and growth of ZrO2 to form TSLCZ. In contrast, reflux route leads to an unstable lamellar structure and non-crystalline inorganic phase, while hydrothermal route promotes the crystallization but cannot gain any ordered nanostructures. Moreover, neither reflux route nor hydrothermal route can obtain TSLCZ. The possible synthesis mechanism of TSLCZ via this novel R-HT route was proposed and discussed. (C) 2012 Elsevier B.V. All rights reserved.