Hollow spheres of mesostructured lead titanate, denoted as PTM-1, have been prepared via a combined oil-in-water emulsion mediated and neutral amine supermolecular templated route. The variety of reaction temperatures and KOH concentrations indicates hollow spheres can be formed under a very critical condition. The structure and composition of the as-synthesized PTM-1 have been determined by powder X-ray diffraction, high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDS), CHN (carbon-hydrogen-nitrogen) elemental analysis, and thermal analysis. Chemical extraction of organic templates by a cosolvent of weak acid and alcohol has resulted in the formation of a new mesoporous material of non-silica oxide with high porosity.