The present review discusses the chemistry of thexylborane pertinent to organic synthesis, and summarizes scattered results of organic synthesis involving thexylborane. 1.Chemistry of Thexylborane 1.1. Preparation and Characterization of Thexylborane 1.2. Reaction of Thexylborane with Olefins 2. Synthetic Applications of Thexylborane 2.1. Synthesis of Unsymmetrical Ketones - A Multi-Carbon Homologation of Olefins 2.2. Synthesis of Cyclic Ketones - A New Annelation Reaction 2.3. Coupling of Two Unlike Alkyl Groups via Bromination of Thexyldialkylboranes 2.4. Synthesis of trans-Disubstituted Olefins 2.5. Syntheses of Conjugated Dienes 2.6. Stereoselective Syntheses of Diols from Dienes 2.7. Synthesis of 1,5-Diols from Monoolefins 2.8. Synthesis of Monoalkylboranes as Triethylaminates 2.9. Selective Reduction with Thexylborane 2.10.Selective Reduction with Trialkylborohydrides Containing the Thexyl Group