Constructing three-dimensional (3D) heterostructures with fast electrochemical reaction kinetics is of great importance in energy storage and conversion, yet remains huge challenges. Herein, we report the design and construction of a family of hierarchically architecture comprising of glucose-modified layered double hydroxides nanosheets wrapped Co3O4 nanowire arrays on Ni foam (CIML-m; I=Ni, Co; M=Mn, Co, Al; Ni foam=NF) for high-performance electrodes. LDH-m nanosheet with expanded interplanar spacing resulted from the glucose molecule intercalation is more favorable for the diffusion of ions, further boosting the electrochemical performance. Benefiting from this feature, the optimal 3D core-shell Co3O4@NiMn LDH (CNMnL-m) architectures exhibits an excellent pseudocapacitive performance of 1644 F g(-1) at 1 A g(-1) with excellent cycling stability of 94.2% over 5000 cycles. Such heterostructure exhibits an excellent practical use when employed as a positive electrode in an asymmetric supercapacitor with high energy density of 38.4 W h kg(-1) at power density of 800 W kg(-1). Given the method's generality, this work opens new avenues in controlled design and synthesis of 3D core-shell heterostructures for developing high-performance electrodes in energy storage and conversion.