Ultralong ZnS nanowires with high purity were grown on Au-coated polar C face of 6H-SiC substrates via metalorganic chemical vapor deposition at low temperatures. The ZnS nanowires have zinc-blende structure and the length is up to tens of micrometers. HRTEM investigations show that the nanowires are well crystalline single crystal grown along [1 1 1] and free of bulk defects. However, sparse straight and curved nanowires with poor crystalline nature are randomly grown on the Au-coated Si face of 6H-SiC substrates. We deduce that the growth of ZnS is related to the substrates and C face can enhance Au-catalytic VLS growth. The CL spectra of an individual nanowire grown on C and Si face reveal different optical properties. Intrinsic sulfur and zinc vacancies are the main reasons for the 458.1 nm and 459.2 nm blue emission detected in the nanowire grown on C face and Si face, respectively. Nevertheless, an unusual green emission at 565.1 nm is observed in the poor crystalline nanowire grown on Si face, which originates from the bulk defects. (C) 2011 Elsevier Ltd. All rights reserved.