A novel three‐dimensional kenaf‐stem‐derived macroporous carbon (3D‐KSC)/reduced graphene oxides (rGO) integrated electrode was constructed as a supporting matrix to deposit CuO−Co bimetallic nanostructures (CuO‐CoNSs) for electrochemical sensing of glucose. The rGO and CuO‐CoNSs were firmly grown on the channels of 3D‐KSC step‐by‐step to construct the CuO‐CoNSs/rGO/3D‐KSC integrated electrode. The obtained CuO‐CoNSs/rGO/3D‐KSC integrated electrode was carefully characterized with several techniques, such as SEM, Raman spectroscopy, FTIR, XRD, XPS, and electrochemistry. The results showed that lots of rGO covered the macropores of 3D‐KSC, which avoided the aggregation of rGO effectively and improved the utilization efficiency of 3D‐KSC. A large number of dendritic CuO‐CoNSs were subsequently grown in the macropores of the rGO/3D‐KSC integrated electrode. Owing to the hierarchical configuration, the CuO‐CoNSs/rGO/3D‐KSC integrated electrode showed superior performances for non‐enzymatic electrochemical glucose sensing with a suitable linear range (0.01–3.95 mM) and high sensitivity of 802.86 μA mM−1 cm−2. The result demonstrated that the electrode was suitable for detecting glucose in bodily fluids. The rGO/3D‐KSC might also be applied to load other NSs or enzymes for electrochemical sensing.