Cadmium sulphide (CdS) nanowires with a monodisperse diameter of 3.6 nm and an aspect ratio of 10-170 were successfully synthesized using a simple and reproducible hot coordinating solvents method. The morphology and optical properties of the CdS nanocrystals were investigated using transmission electron microscopy (TEM), high-resolution TEM (HRTEM) ultraviolet-visible (UV-Vis) absorption spectroscopy and photoluminescence (PL) spectroscopy. It was found that using a long alkyl chain phosphonic acid-octadecylphosphonic acid (ODPA) causes a low diffusion rate and low reactivity which help to control the morphology of the nanocrystals. The timing of the injection process was also found to have critical effect on the morphology of the nanocrystals. Sharp peaks in both the UV-Vis absorption and PL spectra indicate that the size distribution of the diameter is nearly monodisperse. The photovoltaic properties of photovoltaic devices made with a blend of our nanowires and poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylenel (MEH-PPV) were also investigated. Devices made with the nanowires were found to have double the I(sc) observed in devices made with lower aspect ratio CdS nanorods. The possible reason of low photocurrent and high V(oc) is maybe due to the presence of ligand in the nanocrystals. (C) 2009 Elsevier B.V. All rights reserved.