A hierarchical structure of thermally stable macroporous zirconium phosphate solid acids with supermicroporous walls was prepared by a simple self-assembly process from the precursors of zirconium propoxide and orthophosphoric acid solution. The macroporous structures are uniform with the diameters ranging from 300 to 800 nm, one-dimensional channel-like. The effect of surfactant Brij 56 on the formation of macroporous structures has been studied. The frameworks of the synthesized hierarchical zirconium phosphates ate amorphous with Zr-O-P bonding, exhibiting remarkably high thermal stability (at least 800 degrees C), on the basis of the X-ray diffraction (XRD), N-2 adsorption, X-ray photoelectron spectroscopy (XPS) analysis, Fourier transform infrared (FT-IR) and P-31 nuclear magnetic resonance (NMR) spectra. Larger quantities of Zr-OH and P-OH groups are observed besides surface hydroxyl groups, suggesting the presence of acidity and the possibility of surface functionalization for practical applications including catalysis. The macroporous zirconium phosphates with hierarchical structures could also be the potential and efficient catalyst supports for the design of the structured catalysts and reactors. (c) 2005 Elsevier B.V. All rights reserved.