Hierarchical biomorphic ZnO films are prepared by a simple soakage procedure associated with succedent calcination treatment, using natural eggshell membrane (ESM) as the template. The hierarchy of ESM architecture is faithfully achieved by the assembly of ZnO nanocrystallites into interwoven meshwork at three dimensions. The thermal evolution, phase, morphology and pore size distribution of the samples are characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, field emission gun scanning electron microscopy (FESEM) and nitrogen isothermal adsorption measurement. Based on the detailed investigation, a possible synthesis mechanism is discussed here. (C) 2007 Elsevier B.V. All rights reserved.