A facile approach of evaporation-induced self-assembly plus coating was developed using nonwoven fabrics (NF) as a sacrificial scaffold, leading to the acquisition of hierarchically macro/mesoporous alumina monolith. The macropores templated by NF show a tubular structure of about 10 mu m in channel diameter. The monolith is composed of ordered mesostructured wall with large-sized mesopores and high thermal stability. The regularity of the mesopores can be maintained up to 900 degrees C, even after the amorphous Al2O3 transforms to crystalline structure (gamma-Al2O3). This facile route can be extended to the preparation of other hierarchically macro/mesoporous monoliths such as TiO2, ZrO2, ZnO, et al.