Designing ingenious and stable carbon nanostructures is critical but still challenging for use in energy storage devices with superior electrochemistry kinetics, durable capacitive activity, and high rate survivability. To pursue the objective, a simple self-assembly strategy is developed to access carbon superstructures built of nanoparticle embedded plates. The carbon precursors, 2,4,6-trichloro-1,3,5-triazine and 2,6-diaminoanthraquinone can form porous organic polymer with “protic salt”-typed rigid skeleton linked by −NH2+Cl−− “rivets”, which provides the cornerstone for hydrogen-bonding-guided self-assembly of the organic backbone to superstructures by π−π plane stacking. The ameliorative charge density distribution and decreased adsorption energy in as-fabricated carbon superstructures allow the high accessibility of the build-in protophilic sites and efficient ion diffusion with a low energy barrier. Such superstructures thus deliver ultra-stable charge storage and fast proton-coupled redox kinetics at the structural−chemical defects, contributing to unprecedented lifespan (1,000,000 cycles), high-rate capability (100 A g−1) for carbon-based supercapacitors, and an ultrahigh energy density (128 Wh kg−1) for Zn-ion hybrid supercapacitors. The self-assembled carbon superstructures significantly improve the all-round electrochemical performances, and hold great promise for efficient energy storage.