 This paper presents a new and simple method for high-rate performance of PANI/Co3O4–CuO (PANI/MO–M′O′) raspberry via the sol–gel method and compares structural and electrochemical characteristics of both Co3O4–CuO (MO–M′O′) nanomatrix and PANI/MO–M′O′ raspberry nanoarray. Using the PANI/MO–M′O′ raspberry-inspired anode in lithium-ion batteries (LIBs) resulted in the improved electrochemical performances of cycling stability, discharge capacity, and rate capability compared with the MO–M′O′ nanomatrix. In addition, regarding anode material for LIBs, PANI/MO–M′O′ anode presented the specific capacity of 455.34 mAh g−1 at the current density of 1.0 A g−1 after 60 cycles. Further, the PANI/MO–M′O′ nanoarray produced a satisfied discharge capacity of 311.22 mAh g−1 at a density of 3.0 A g−1, as well as an appropriate cycle stability and rate capability. Finally, the improved electrochemical property of this unique organic–inorganic heterostructure (PANI/MO–M′O′ raspberry design) can be related to the avoid aggregation, an effective electric contact, improved electrochemical stability, and a lower charge-transfer resistance during cycling performance. These advantages are mainly because of the novel catalytic role of the PANI electron transfer in the PANI/MO–M′O′ raspberry as a new anode material.