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It is desirable to design nonprecious metal nanocatalysts with high stability and catalytic performance for fine chemicals production. Here, a method is reported for the preparation of cobalt metal and cobalt oxide cores confined within nanoporous nitrogen‐doped hollow carbon capsules. Core–shell structured Zn/Co‐ZIF@polymer materials are fabricated through a facile coating polymer strategy on the surface of zeolitic imidazolate frameworks (ZIF). A series of hollow carbon capsules with cobalt metal and cobalt oxide are derived from a facile confined pyrolysis of Zn/Co‐ZIF@polymer. The hollow Co‐CoOx@N‐C capsules can prevent sintering and agglomeration of the cobalt nanoparticles and the nanoporous shell allows for efficient mass transport. The specific surface area and Co particle size are optimized through finely tuning the original Zn content in ZIF particles, thus enhancing overall catalytic activity. The yolk–shell structured Zn4Co1Ox@carbon hollow capsules are shown to be a highly active and selective catalyst (selectivity >99%) for hydrogenation of nitrobenzene to aniline. Furthermore, Zn4Co1Ox@carbon hollow particles show superior catalytic stability, and no deactivation after 8 cycles of reaction. The hollow Co‐CoOx@N‐C capsules may shed light on a green and sustainable catalytic process for fine chemicals production. [ABSTRACT FROM AUTHOR]