In this work, TiO2 nano-octahedron and nano-rods were successfully synthesized, and Cu oxides were loaded on them. Structures of CuO/TiO2 catalysts were studied by XRD, TEM, and Raman techniques. It was founded that TiO2 nano-octahedron and nano-rods dominantly exposed (101) and (100) facets of TiO2, respectively. Cu cations located in tetrahedral vacant sites on (101) facet of TiO2 and coordinated with 4 neighbor oxygen, whereas it located in octahedral vacant sites on (100) facet of TiO2 and coordinated with 6 neighbor oxygen, which resulted in redox cycle Cu2+ +Ti3+ <--> Cu+ + Ti4+ and more acid sites on surface of CuO/TiO2 nano-octahedron, and thus the enhanced NH3-SCR performance.