Disclosed is a natural-superlattice homologous single-crystal thin film, which comprises a complex oxide which is epitaxially grown on either one of a ZnO epitaxial thin film formed on a single-crystal substrate, the single-crystal substrate after disappearance of the ZnO epitaxial thin film and a ZnO single crystal. The complex oxide is expressed by the a formula: M1M2O3 (ZnO)m, wherein M1 is at least one selected from the group consisting of Ga, Fe, Sc, In, Lu, Yb, Tm, Er, Ho and Y, M2 is at least one selected from the group consisting of Mn, Fe, Ga, In and Al, and m is a natural number of 1 or more. A natural-superlattice homologous single-crystal thin film formed by depositing the complex oxide and subjecting the obtained layered film to a thermal anneal treatment can be used in optimal devices, electronic devices and X-ray optical devices.