Biomorphic porous ZnO nanostructures were successfully synthesized via an aqueous sol-gel soaking process using pieces of apple flesh and skin as templates and employed for glucose direct electrochemical biosensor. The structure and morphology of ZnO nanostructures were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). By modifying glassy carbon electrode with the biomorphic ZnO nanostructures and Nafion, two glucose biosensors were constructed and their direct electrochemistry of glucose oxidase (GOD) was successfully investigated by cyclic voltammetry (CV). The biomorphic porous ZnO nanostructures using apple skin template (S-ZnO) were more effective in facilitating the electron transfer of immobilized GOD than that of using flesh apple template (F-ZnO). This may be a result of the unique morphology and smaller average crystallite size of the S-ZnO nanostructure. GOD immobilized on Nafion-porous S-ZnO nanostructure composite display direct, reversible, and surface-controlled redox reaction with a detection limit of 10 mu M, a response time of 7 s, high sensitivity of 23.4 mu A/mM cm(2) and a fast heterogeneous electron transfer rate with a rate constant (k(s)) of 3.9 s(-1). It was found that S-ZnO significantly has improved the direct electron transfer between GOD and glassy carbon electrode with good stability and reproducibility. (C) 2012 Elsevier B. V. All rights reserved.