Biomorphic Cr2O3 was synthesized using two different wood tissues as templates and was subjected to X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, and nitrogen adsorption measurements to investigate the phases and microstructures. A hierarchical pore structure from the ordered pore arrays derived from wood tissues to the nanopores formed on ceramic struts is demonstrated. The microstructure of the ceramic struts changed with increasing calcination temperature. From Fourier transform infrared spectroscopy, characteristic IR absorption peaks were detected, and furthermore, an overall collapse of transmission curves with increasing calcination temperature was observed.