Herein, a copper(I)‐catalyzed asymmetric hydrophosphination of 3,3‐disubstituted cyclopropenes is uncovered, which provides a series of phosphine derivatives in high to excellent diastereo‐ and enantioselectivities. The methodology enjoys broad substrate scopes on both 3,3‐disubstituted cyclopropenes and diarylphosphines. The high stereoselectivity is attributed to both the high stability of Cu(I)‐(R,R)‐QUINOXP* complex in the presence of stoichiometric HPPh2 and the produced phosphines and the high‐performance asymmetric induction of the Cu(I)‐(R,R)‐QUINOXP* complex. Finally, the method is used for the synthesis of new chiral phosphine‐olefin compounds built on a cyclopropane skeleton, one of which serves as a wonderful ligand in Rh‐catalyzed asymmetric conjugate addition of phenylboronic acid to various α,β‐unsaturated compounds.