Abstract: Borane is a class of boron compounds, including active small borane molecules and relative stable polyhedral borane compounds, and has widely applied in energy storage, material science, and pharmaceutical medicine, especially as promising boron carriers for boron neutron capture therapy(BNCT), and many other fields. The synthesis of new borane molecules and optimization of the synthetic methods of boranes have been a significant part of boron chemistry over the last one hundred years. Herein, we have systematically summarized the syntheses of small borane molecules, polyhedral boranes, and carboranes; we also provided the molecular structures and ¹¹B NMR spectra of borane compounds. Anticipatedly, this review will provide the basic knowledge for readers interested in borane chemistry and facilitate the readers for improving the synthetic methods of boranes and exploring the application of borane compounds.