Display omitted •A 3D hydrangea-like ZnCo2O4/NiCoGa-layered double hydroxide@polypyrrole core–shell heterostructure was successfully constructed.•Density functional theory (DFT) calculations were adopted to authenticate the charge redistribution at the heterointerfaces.•ZnCo2O4/NiCoGa-layered double hydroxide@polypyrrole exhibits satisfactory electrochemical performance for supercapacitors. Rationally constructing advanced battery-type electrodes with hierarchical core–shell heterostructure is essential for improving the energy density and cycling stability of hybrid supercapacitors. Herein, this work successfully constructs hydrangea-like ZnCo2O4/NiCoGa-layered double hydroxide@polypyrrole (denoted as ZCO/NCG-LDH@PPy) core–shell heterostructure. Specifically, the ZCO/NCG-LDH@PPy employs ZCO nanoneedles clusters with large open void space and rough surfaces as the core, and NCG-LDH@PPy composite as the shell, comprising hexagonal NCG-LDH nanosheets with rich active surface area, and conductive PPy films with different thicknesses. Meanwhile, density functional theory (DFT) calculations authenticate the charge redistribution at the heterointerfaces between ZCO and NCG-LDH phases. Benefiting from the abundant heterointerfaces and synergistic effect among different active components, the ZCO/NCG-LDH@PPy electrode acquires an extraordinary specific capacity of 381.4 mAh g−1 at 1 A g−1, along with excellent cycling stability (89.83% capacity retention) after 10,000 cycles at 20 A g−1. Furthermore, the prepared ZCO/NCG-LDH@PPy//AC hybrid supercapacitor (HSC) exhibits a remarkable energy density (81.9 Wh kg−1), an outstanding power density (17,003.7 W kg−1), and superior cycling performance (a capacitance retention of 88.41% and a coulombic efficiency of 93.97%) at the end of the 10,000th cycle. Finally, two ZCO/NCG-LDH@PPy//AC HSCs in series can light up a LED lamp for 15 min, indicating its excellent application prospects.