Highly oriented ZnO nanorods have been grown on various substrates, such as fused silica, Si(100), and sapphire (110), using a simple catalyst-free CVD method at low temperatures. TEM analyses indicate that epitaxial ZnO nanorods have been grown on sapphire (110) with the ZnO/sapphire orientational relationship [001]parallel to[110] and [110]parallel to[001]. In the Si(100) substrate, an amorphous SiOx interfacial layer exists between ZnO nanorods and Si(100). The well-aligned ZnO nanorods on fused silica substrates exhibit a strong UV emission and absorption at around 386 nm under room temperature. Photoluminescence and Raman spectra indicate that there is a very low concentration of oxygen vacancies in the highly oriented ZnO nanorods. Diameter control of the well-oriented and high-quality ZnO nanorods is achievable by variation of the growth conditions.