Synthesis of metal-semiconductor heterostructures may allow the combination of function of the corresponding components and/or the enhanced performance resulting from the interactions between all the components. In this paper, Au@Cu2Ocore-shell heterostructures are prepared by a seed-growth method, using different-shaped Au nanocrystals as the seeds such as nanorods, octahedra, decahedra, dots, and nanocubes. The results revealed that the final structure of Au@Cu2Owas greatly influenced by the shape of the seeds used. Exposure of Cu2O{111}and Cu2O{001}favored when the overgrowth happened on Au{111}and Au{001}surface, respectively. The size of the product can also be tuned by the amount of the seeds. The results reported here provide a thinking clue to modulate the shape and size of core-shell nanocrystals, which is useful in developing new materials with desired performance.