An efficient C-P coupling reaction of enantiopure tert-butylmethylphosphine-boranes with aryl and heteroaryl halides is developed by using Pd(OAc)2/dppf as a catalyst, affording a series of (S) or (R)-P-chiral phosphines in moderate to high yields and with ee values up to 99% ee. Moreover, the reaction time could be reduced from 72 h to 6 h with increased ee values under microwave irradiation.