The highly catalytic asymmetric -hydroxylation of β-indanone esters and β-indanone amides using peroxide as the oxidant was realized with a new C-2′ substituted Cinchona alkaloid derivatives. The two enantiomers of -hydroxy-β-indanone esters could be obtained by simply changing the oxidant. This protocol allows a convenient access to the corresponding -hydroxy-β-indanone esters and -hydroxy-β-indanone amides with up to 99% yield and 98% ee.