Free-standing multiwall carbon nanotubes (MWNTs) films were coated, using chemical vapor deposition method, with a thin layer of nanostructural ZnO. The morphology and crystal structure of the as-grown products were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman scattering analyses. Field emission (FE) results demonstrated that the needle-like and spherical ZnO MWNTs composite structure films possessed good performance with a turn-on field of 1.3, 2.2 V mu m (1) and a threshold field of 2.6, 4.5 V mu m (1), respectively. The glucose-sensing characteristic has also been studied. The multi-layer electrode (PDDA/GOx/ZnO/MWNTs) exhibited significant electrocatalysis to the oxidation and reduction of H2O2 than the PDDA/GOx/MWNTs electrode, which provided wide potential applications in clinical, environmental, and food analysis. (C) 2009 Elsevier B.V. All rights reserved.