As an efficient catalyst for asymmetric transfer hydrogenation reaction (ATH reaction) of α,β-unsaturated ketones, Rh-Cp ∗ –TsDPEN (Cp ∗ =1,2,3,4,5-pentamethylcyclopenta-1,3-diene, TsDPEN=N-(p-toluenesulfonyl)-1,2-diphenyl- ethylenediamine) shows high chemoselectivity on CO and CC reduction. In our method, both CO and CC bonds in a variety of chromenone derivatives were reduced efficiently in aqueous media, resulting in at least 98% ee and up to 99% yields in a convenient way without further purification. The product was a useful intermediate for deriving chiral chroman-4-amine, which was reported as an effective agent against hypotension and inflammatory pain by inhibiting human bradykinin B1 receptor.