ZnO single crystal nanohexagons have been grown heteroepitaxially on p-type Si-face 4H-SiC substrates with 8 degrees miscut from to [0 0 0 1] by catalyst-free atmospheric pressure metalorganic chemical vapor deposition and characterized by x-ray diffraction, scanning and transmission electron microscopy as well as energy disperse x-ray and cathodoluminescence analyses. The as-grown ZnO nanohexagons have a pillar shape terminated by a and c plane facets, and are aligned along the growth direction with the epitaxial relation [0 0 0 1](ZnO) parallel to[0 0 0 1](4H-SiC) and [1 0 (1) over bar 0](ZnO) parallel to[1 0 (1) over bar 0](4H-SiC). The ZnO nanohexagons demonstrate intense UV emission (lambda(NBE)=376 nm) and negligible defect-related luminescence. (c) 2009 Elsevier B.V. All rights reserved.