AbstractIn this work a green route is reported to prepare a TiO2 macroporous network using corn starch microspheres flake as a bio-template. The starch microspheres prepared by emulsion technology were used as a template into which precursor tetrabutyl titanate (TBOT) was permeated using supercritical carbon dioxide (scCO2) as a forceful carrier or infiltration media, resulting in the formation of an organic/inorganic hybrid material; then the coated template was gelled and dried during the scCO2-coating and the depressurization processes, followed by removal of the template by calcination at 700°C; finally, TiO2 inverse-opals-like material reversely replicating the starch microspheres template was obtained. Scanning electron microscopy (SEM), nitrogen sorption measurements, and X-ray diffraction (XRD) indicated that the products were the inverse replicas from their templates. The obtained TiO2 inverse opals-like material showed a wide dispersion of pore sizes from mesopores to macropores – a few nanometers to several micrometers –with the BET surface area up to 103 m2/g, and a predominantly anatase crystalline phase. In addition, the wall thickness of the macropores varied with tunable pressure for closed cells or open-cell foams. So this facile and environmentally friendly process for the preparation of high-surface area, thermally-stable, metal-oxide catalysts and supports by a starch microsphere templating approach may have widespread potential applications in catalysis, absorbents, photoelectric materials, and so on.