Monodispersed ZrO2 precursor nanoparticles with a diameter of 25 nm were successfully synthesized by using diglycol as complexing reagent. The kinetic of particle growth as a function of concentration ratio of ZrOCl2: diglycol was investigated. The as-synthesized ZrO2 precursor nanoparticles were homogenously coated on the surface of polystyrene particles. Multilayer coating process was implemented by using poly (acrylic acid) (PAA) to modify the surface charges of the coated spheres, which was characterized by zeta-potential, particles size distribution and microstructural observation. The multilayer-coated polystyrene (PS) spheres have been used as templates to produce macroporous materials. Ordered macroporous ZrO2 materials were obtained after the ZrO2 precursor nanoparticles coated PS spheres were formed by centrifugation and calcined at 550 degrees C for 3 h. The porous wall thickness could be well controlled by using the multilayer nano-ZrO2 coated PS spheres with different coating thickness. (c) 2006 Springer Science + Business Media, Inc.