As one of the most active rare earth, CeO2 has been receiving considerable attention due to its multifunctional properties. Herein, we present a facile and green route toward hierarchical N-doped CeO2 hollow microcapsule by using hemerocallis pollen as biotemplate. The resulting sample was characterized by X-ray diffraction spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, nitrogen adsorption and desorption, UV-Vis diffuse reflectance spectra and X-ray photoelectron spectrogram. The obtained N-doped CeO2 microcapsule exhibits much more superior photocatalytic activity for the hydrogen generation by water splitting, which owing to the nitrogen doping and structural features. This facile method of research provides a rational approach to replicate desired biological structures for semiconductor nanoparticle catalysis in other potential areas. (C) 2017 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.