Abstract: | Cost‐effective metal‐based nanostructured hybrids have been widely dedicated to potential energy storage and conversion applications. Herein, we develop a facile methodology for the synthesis of precise carbon‐confined hybrid nanostructures by stereoselective assembly accompanied by catalytic pyrolysis. Polyacrylonitrile fiber films favors not only metal‐polymer coordination, but also oriented assembly to ensure the well‐defined nanostructure of the carbon hybrids. During chemical vapor deposition (CVD), cobalt‐nanoparticle‐catalyzed growth of carbon‐nanotube branches driven by organic molecules (e.g. melamine) delivers hierarchical carbon hybrids. The resulting carbon hybrids exhibit outstanding electrochemical performance for metal‐ion batteries, for example, a high specific capacity of 680 mAh g?1 after 320 cycles (Li‐storage) and 220 mAh g?1 after 500 cycles (Na‐storage) without decay. |