A Cu-catalyzed enantio- and diastereoselective diarylmethylation of 1,3-dicarbonyl compounds is described. It is a successful example of constructing all-carbon quaternary stereocenters from 3 °C–H nucleophiles, a challenging topic in synthetic chemistry. In the present work, two contiguous stereocenters are constructed with high levels of stereoselectivity and atom economy. The broad scope of 1,3-dicarbonyl nucleophiles and the tolerance of a wide range of functional groups make this protocol of great importance in the synthesis of chiral diarylmethane compounds.