In this paper, we report a simple solid-state method for fabricating cobalt-oxide–carbon core-shell nanostructures. With this technique, various forms of nanocarbons such as nanotubes, polyhedrons and onions can be generated via pyrolyzing cobalt–complex xerogels at 150 ~ 340°C. The thus-formed nanocarbons can be protected by cobalt-oxide matrix up to 1000°C in air atmosphere. Cobalt-oxide shelled or unshelled nanocarbons can be controlled by choosing a suitable complexing agent for the xerogel precursors. In particular, glycine has been proven to be a good complexing agent for low-temperature formation of unshelled nanocarbons and high-temperature generation of shelled nanocarbons.