HighlightsProposing a one-step pyrolysis strategy to fabricate a novel bilayer-shelled N, O-doped hollow porous carbon microspheres (NOHPC) anode.The optimized NOHPC anode displays a high K-storage capacity of 325.9 mAh g−1at 0.1 A g−1and excellent rate performance (201.1 mAh g−1at 5 A g−1after 6000 cycles).The assembled NOHPC//hollow porous activated carbon microspheres (HPAC) potassium ion hybrid capacitors deliver a high energy density of 90.1 Wh kg−1at a power density of 939.6 W kg−1even over 6000 cycles.Supplementary InformationThe online version contains supplementary material available at 10.1007/s40820-023-01113-6.