The selective oxidation of propylene with O2 to propylene oxide and acrolein is of great interest and importance. We report the crystal-plane-controlled selectivity of uniform capping-ligand-free Cu2 O octahedra, cubes, and rhombic dodecahedra in catalyzing propylene oxidation with O2 : Cu2 O octahedra exposing {111} crystal planes are most selective for acrolein; Cu2 O cubes exposing {100} crystal planes are most selective for CO2 ; Cu2 O rhombic dodecahedra exposing {110} crystal planes are most selective for propylene oxide. One-coordinated Cu on Cu2 O(111), three-coordinated O on Cu2 O(110), and two-coordinated O on Cu2 O(100) were identified as the catalytically active sites for the production of acrolein, propylene oxide, and CO2 , respectively. These results reveal that crystal-plane engineering of oxide catalysts could be a useful strategy for developing selective catalysts and for gaining fundamental understanding of complex heterogeneous catalytic reactions at the molecular level.