Smart construction of advanced anode materials is extremely critical to develop high-performance lithium ion batteries. In this work, we have reported a facile strategy for fabricating Co3O4/polyaniline (PANI) core–shell arrays (CSAs) by chemical bath deposition (CBD) + electrodeposition methods Electrodeposited PANI shell is intimately decorated on the CBD-Co3O4 nanorods forming composite CSAs. Highly conductive network and stress buffer layer are achieved with the aid of tailored PANI shell. Due to these advantages above, the designed Co3O4/PANI CSAS exhibit good electrochemical performance with higher reversible capacity (787mAhg−1) and better cycle stability than the unmodified Co3O4 counterpart. Our results show a new way for preparing advanced inorganic-organic composite electrodes for electrochemical energy storage.