In this work, we prepared a novel structure comprising of raspberry-like CeO2 deposited on CuO microspheres (Ce-CuO) for Rochow reaction. The synthesis was carried out via a facile one-pot hydrothermal reaction without using any template, in which, the basic copper carbonate microspheres were first formed via self-assembly of basic copper carbonate nanorods, followed with deposition of cerium hydroxide. After calcination, they were transformed into Ce-CuO but still maintained the hierarchical structure, and meanwhile, mesoporous structure was formed (for simplicity, we will only state them as metal oxide in the following context). The samples were characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM), and scanning electron microscopy (SEM) techniques. When used as a Cu-based catalyst, Ce-CuO exhibited superior catalytic property to the single CuO, CeO2 and their physically mixture in the Rochow reaction with dimethyldichlorosilane (M2) selectivity increased from ca. 65 to 83.7%. The higher M2 selectivity of Ce-CuO is mainly due to its larger surface area and the synergistic effect between CuO and CeO2. This work demonstrates that catalytic performance of the Cu-based can be improved by adding Ce rare-earth element and by carefully controlling their structures. Crown Copyright (C) 2015 Published by Elsevier B.V. All rights reserved.