In this work we synthesized two inverse kinds of cobalt and zinc oxide nanocomposites (CoO/ZnO and Zn1-xCoxO/Co 1-yZnyO) and compared methodologistic features observed from the syntheses. The binary oxide system chosen herein is because divalent cobalt and zinc have very similar ion radii, and they interdiffuse easily when forming doped structures. A "two-pot" process was devised for the CoO/ZnO composites, in which mesocrystalline cores of CoO were formed first, followed by introduction of an overlayer of ZnO nanoparticles to the core surfaces. In contrast, a "one-pot" process was developed for the Zn1-xCoxO/Co1-yZnyO composites. In particular, hollow and/or multishelled Zn1-xCoxO cores (in wurtzite phase) serve as a support for the nanospheres of Co 1-yZnyO (in rock-salt phase) in this latter method. Our findings indicate that while "multi-pot" synthesis is a prevailing methodology for composite nanoparticles, simpler "one-pot" synthesis can be an effective approach for preparation of more complex nanocomposite materials, especially for interdoped metal oxides. As an example, our as-prepared binary oxide composites Zn1-xCoxO/Co 1-yZnyO have shown good catalytic activity for oxidation of carbon monoxide at relatively low reaction temperatures. © 2009 American Chemical Society.