The highly regio-and stereoselective hydroborations of unactivated internal alkynes with diboron compound catalyzed by Cu(OTf)_2 with spiro(phosphoamidite) as ligand in the presence of Cs_2CO_3 in water was developed.This protocol was applied efficiently in the aqueous synthesis of multi-substituted vinylboranes. The highly regio-and stereoselective hydroborations of unactivated internal alkynes with diboron compound catalyzed by Cu (OTf) _2 with spiro (phosphoamidite) as ligand in the presence of Cs_2CO_3 in water was developed. This protocol was applied efficiently in the aqueous synthesis of multi- substituted vinylboranes.