The chemistry of frustrated Lewis pairs (FLPs) provides the most important approach for the metal‐free hydrogenation and hydrosilylations. Great progress has been achieved in this area for the past decade. Some promising results have also been obtained. This perspective article mainly focuses on the recent advances for the synthesis of chiral Lewis acidic boranes in category of three protocols, 1) hydroboration of chiral internal alkenes with Piers’ borane HB(C6F5)2; 2) in situ hydroboration of chiral alkenes or alkynes without any purification; 3) and substitution reaction of (C6F5)nBCl3–n with chiral organometallic reagents, as well as their applications in the metal‐free asymmetric hydrogenations and hydrosilylations.