In this work, a novel hierarchical porous ZnO is successfully synthesized through a sol gel method, in which a kind of biological material is used as hard template, block copolymer Pluronic F127 as soft template. The phase and morphology of the products are characterized by X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), and transmission electron microscope (TEM). The results show that the as-prepared ZnO with a hierarchical porous architecture is assembled by multiple-layered porous nanosheets, of which the pore structure is highly ordered. The photocatalytic activity of the as-prepared ZnO is evaluated by photodegradation reaction of methylene blue. The photoelectrochemical (PEC) property of the hierarchical porous ZnO film is also investigated in this work. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.