Recently, single layer MoS2 with a direct band gap of 1.9 eV has been proposed as a candidate for two dimensional nanoelectronic devices. However, the synthetic approach to obtain high-quality MoS2 atomic thin layers is still problematic. Spectroscopic and microscopic results reveal that both single layers and tetrahedral clusters of MoS2 are deposited directly on the SiO2/Si substrate by chemical vapor deposition. The tetrahedral clusters are mixtures of 2H- and 3R-MoS2. By ex situ optical analysis, both the single layers and tetrahedral clusters can be attributed to van der Waals epitaxial growth. Due to the similar layered structures we expect the same growth mechanism for other transition-metal disulfides by chemical vapor deposition. © 2013 The Royal Society of Chemistry.