Light alkali metal hydridotriphenylborates M[HBPh3] (M = Li, Na, K), characterized as, tris{2-(dimethylamino)ethyl}amine (L) complexes [(L)M][HBPh3], act as efficient catalysts for the chemoselective hydroboration of a wide range of aldehydes and ketones using pinacolborane HBpin. The lithium derivative showed a remarkably high TOF of >= 17 s(-1). These compounds also catalyze the hydroborative reduction of CO2 to give, formoxyborane HCO(2)Bpin without any over-reduction.