Antimony telluride (Sb2Te3) thin films were prepared by a room temperature Metal–Organic Chemical Vapor Deposition (MOCVD) process using antimony chloride (SbCl3) and bis(trimethylsilyl)telluride (Te(SiMe3)2) as precursors. Pre-growth and post-growth treatments were found to be pivotal in favoring out-of-plane and in-plane alignment of the crystallites composing the films. A comprehensive suite of characterization techniques were used to evaluate their composition, surface roughness, as well as to assess their morphology, crystallinity, and structural features, revealing that a quick post-growth annealing triggers the formation of epitaxial-quality Sb2Te3 films on Si(111).