<p>Carbon superstructures with multiscale hierarchies and functional attributes represent an appealing cathode candidate for zinc hybrid capacitors, but their tailor-made design to optimize the capacitive activity remains a confusing topic. Here we develop a hydrogen-bond-oriented interfacial super-assembly strategy to custom-tailor nanosheet-intertwined spherical carbon superstructures (SCSs) for Zn-ion storage with double-high capacitive activity and durability. Tetrachlorobenzoquinone (H-bond acceptor) and dimethylbenzidine (H-bond donator) can interact to form organic nanosheet modules, which are sequentially assembled, orientally compacted and densified into well-orchestrated superstructures through multiple H-bonds (N–H···O). Featured with rich surface-active heterodiatomic motifs, more exposed nanoporous channels, and successive charge migration paths, SCSs cathode promises high accessibility of built-in zincophilic sites and rapid ion diffusion with low energy barriers (3.3 Ω s^−0.5). Consequently, the assembled Zn||SCSs capacitor harvests all-round improvement in Zn-ion storage metrics, including high energy density (166&#xa0;Wh&#xa0;kg⁻¹), high-rate performance (172&#xa0;mAh&#xa0;g⁻¹ at 20&#xa0;A&#xa0;g⁻¹), and long-lasting cycling lifespan (95.5% capacity retention after 500,000 cycles). An opposite charge-carrier storage mechanism is rationalized for SCSs cathode to maximize spatial capacitive charge storage, involving high-kinetics physical Zn²⁺/CF₃SO₃⁻ adsorption and chemical Zn²⁺ redox with carbonyl/pyridine groups. This work gives insights into H-bond-guided interfacial super-assembly design of superstructural carbons toward advanced energy storage.</p>