Highly enantioselective hydroboration method of 1,1-disubstituted alkenes has been developed. This reaction provides an efficient synthetic method of enantioenriched β-borylalkanes. In the presence of DTBM-Segphos-ligated Cu catalyst, a range of 1,1-disubstituted alkenes with an alkyl, aryl, silyl, amine substituent produced alkylboron compounds in good yields and excellent enantioselectivitys up to 99% ee. Furthermore, catalyst loading as low as 1 mol% could be furnished desired product without decrease of yield and selectivity.