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[Display omitted] • The Cl-doped ZIF-67-derived carbon microspheres were prepared by a novel chlorination method in high-temperature. • The electrochemical performance of CCH@CM has been greatly improved compared to ZIF-67. • CCH@CM continues the microporous structure of ZIF-67 while minimizes volume expansion. • Cobalt Chloride Hydrate (CCH) grown in situ provides maximum active sites for electrochemical reactions with Li-ions. In this work, the carbon-microsphere loaded with cobalt chloride hydrate (CCH@CM) was prepared via a collaborative and chlorination strategy derived from ZIF-67 precursor, which exhibits a superior electrochemical performance as a lithium-ion battery anode material. The synthesized CCH@CM obtained a high initial discharge capacity (947 mAh g−1) and the capacity attenuation rate is close to zero after 200 cycles at the current density of 100 mA g−1. The porous structure derived from ZIF-67 not only can provide a conductive path, which increases the transport of electrons and lithium ions, but also alleviate volume expansion. The presences of -Cl-/H 2 O groups provide active sites for the anchoring of Li+. As the first successful synthesizing the cobalt chloride hydrate (CCH) from ZIF-67, good electrochemical performance provides a promising for the large-scale application in lithium ion batteries. [ABSTRACT FROM AUTHOR]