Lewis base complexes of borane unlocked the huge potential of reactive and pyrophoric diborane gas. Indeed, borane-THF and borane-SMe2 have become common laboratory reagents. In comparison, due to the strong boron-nitrogen complex and their lack of reactivity, borane-amines are seldom used for organic chemistry applications. Recently there has been an increased interest in borane-amines due to their air- and moisture-stability. They have found several applications as hydrogen storage materials, green hypergolic bipropellants, and precursors to polyaminoboranes, etc. Furthermore, they have been used as reagents for hydroboration, reduction, hydrogenation, reductive amination, borylation, and B-H insertion. Despite these advances, amine-boranes remain very expensive and amine-boranes bearing functional groups are scarce, presumably due to their incompatibility to borane. Current approaches to amine-boranes from amines, such as exchange with borane-Lewis base complexes or metathesis of alkylammonium salts with metal borohydrides, have several drawbacks. We have developed several new procedures for the preparation of amine-boranes, including previously inaccessible borane-intolerant amine-boranes from sodium borohydride. The synthesis and the mechanism of their formation will be discussed. Novel organic chemistry applications of amine-boranes, including those of ammonia borane will also be presented.