Hexagonal (Hx-ZrO2) and lamellar (LrZrO2) phases of zirconium oxide have been prepared using the supramolecular templating approach. Long chain primary alkyl amines led to the formation of lamellar phases, while quaternary ammonium surfactants gave hexagonal phases. The materials have been characterized by XRD, TG/DTG, IR, XPS, SEM and EDX techniques. The influence of various synthesis parameters such as (i) the ZrO2/surfactant ratio, (ii) the surfactant/water ratio, (iii) the nature of surfactant, (iv) the crystallization temperature and (v) the crystallization time have been investigated. The final solid products were found to be thermally unstable regardless of their structure. Removal of the surfactant from the mesopores by solvent extraction without damaging the structure was not possible.