We report on heteroepitaxial fabrication and structural characterizations of ultrafine GaN/ZnO coaxial nanorod heterostructures. The coaxial nanorod heterostructures were fabricated by epitaxial growth of a GaN layer on ultrafine ZnO nanorods. Epitaxial growth and precise control of GaN overlayer thickness were obtained by low pressure metalorganic vapor-phase epitaxy. ZnO nanorods grown on Si and sapphire substrates using catalyst-free metalorganic chemical vapor deposition exhibited diameters as small as 7 nm. Furthermore, structural properties of the coaxial nanorod heterostructures were investigated using both synchrotron-radiation x-ray diffraction and high resolution transmission electron microscopy. (C) 2004 American Institute of Physics.