Porous CeO2 hollow microspheres were successfully prepared through a facile process by using the rape pollen as the biotem-plate. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), the N2 adsorption and desorption, X-ray diffraction (XRD), UV-vis diffuse reflectance spectra, and hydrogen temperature-programmed reduction (H2-TPR) were used for their characterization. The results showed that the obtained materials exhibited the same morphology as that of the pollen template, with a diameter of ca. 10 μm, and the surface was evenly covered with a special network-like structure with mesh size of about 0.3 μm, and the Brunauer-Emmett-Teller (BET) surface area was measured to be 156 m2/g. The detailed property investigation inferred that the product exhibited better photocatalytic activity in acid fuchsine decolorization under daylight because of higher surface area, smaller crystallite size and higher oxygen capacity. Porous CeO2 hollow microspheres were successfully prepared through a facile process by using the rape pollen as the biotem-plate. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), the N2 adsorption and desorption, X-ray diffraction UV-vis diffuse reflectance spectra, and hydrogen temperature-programmed reduction (H2-TPR) were used for their characterization. The results showed that the obtained materials illustrate the same morphology as that of the pollen template, with a diameter of ca. 10 μm , and the surface was evenly covered with a special network-like structure with mesh size of about 0.3 μm, and the Brunauer-Emmett-Teller (BET) surface area was measured to be 156 m2 / g. product introduced better photocatalytic activity in acid fuchsine decolorization under daylight because of higher surface area, smaller crystallite size and higher oxygen capacity.