We report the growth of single-oriented Cu2O (113) film on faceted MgO (110) substrate by radio-frequency plasma assisted molecular beam epitaxy. A MgO {100} faceted homoepitaxial layer was introduced beforehand as a template for epitaxy of Cu2O film. The epitaxial relationship is determined to be Cu2O (113)//MGO(110) with a tilt angle of 4.76 degrees and Cu2O -[1 (1) over bar1]//MgO [1 (1) over bar0] by the combined study of in-situ reflection high-energy electron diffraction and ex-situ X-ray diffraction and transmission electron microscopy. The film demonstrates a good p-type conductivity and excellent optical properties, indicating that this unique approach is potentially applicable for high-index film preparation and device applications. Crown Copyright (C) 2015 Published by Elsevier B.V. All rights reserved.