Rational design and synthesis of hollow core–shell hetero-structures with high complexity still remains challenging for high-performance supercapacitors. Here, a simple and effective strategy that involves a ‘root-etch-wrap’ process was developed to synthesize hollow core–shell hetero-structured electrodes. Specifically, ZnO hollow spheres take root on carbon cloth via an in situ growth routine, then are etched to aid the generation of a ZIF-8 shell. As-synthesized hollow core–shell ZnO@ZIF-8 is wrapped by PANI nanocoating, resulting in a flexible conductive porous electrode (denoted as PANI/ZnO@ZIF-8-CC). The optimized electrode exhibits an ultrahigh areal capacitance (4839–3987 mF cm⁻² at 5–30 mA cm⁻²), which is at least 3 times higher than that of PANI-CC and ZnO@ZIF-8-CC owing to the synergistic effect. In addition, a symmetric flexible supercapacitor fabricated by PANI/ZnO@ZIF-8-CC exhibits a high energy density of 0.137–0.0891 mW h cm⁻³ (at a power density of 1.421–23.629 W cm⁻³) and a good long-term cycling ability (87% for 10 000 cycles at 5 mA cm⁻²). All of these results make unique core–shell structured PANI/ZnO@ZIF-8-CC a promising electrode material for advanced energy storage and conversion applications.