A highly enantioselective carbonyl-ene reaction catalyzed by In(III)-pybox is described. Both 1, 1-disubstituted alkenes and 1,1,2-trisubstituted alkenes proceeded smoothly to give the ene products in high yields up to 97% and with excellent diastereoselectivity and enantioselectivities up to > 99:1 and 99%, respectively.