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NaBr-mediated "bait and switch" mechanism can promote the formation of ZnO, and thus etches carbon matrix around the N -dopants. As a result, the fully formed N -doping and intrinsic carbon defect (N/DC) coupling sites can greatly improve capacitive behavior, so an excellent cycling stability with high reversible capacity is realized. [Display omitted] Coupling sites of nitrogen-dopants and intrinsic carbon defects (N/DC) are highly attractive to improve potassium-storage capacity and cycling stability, yet it is hard to effectively construct them. Herein, a novel strategy is proposed to establish abundant N/DC sites in N -doped carbon (ZIF8/NaBr-1-900) by pyrolyzing the mixture of metal–organic framework (ZIF8)/sodium bromide (NaBr). Systematic investigations disclose that the introduced NaBr can promote the full conversion of Zn-N 4 moieties into zinc oxide (ZnO) via a "bait and switch" mechanism. Such formed endogenous ZnO can etch the carbon matrix of the confined domains around the N dopants during pyrolysis process, and meanwhile the released N -atoms from Zn-N 4 moieties can largely form edge-N. As such, these N/DC coupling sites enable the resultant carbon to have a more significant capacitive behavior related to fast K-ion migration and high structural stability, leading to 255.3 mAh/g at 2 A/g with a prolonged cycle lifespan over 2000 cycles. Moreover, the assembled K-full battery presents a high energy density of 171.2 Wh kg−1 and excellent cyclability over 5000 cycles. This NaBr-mediated endogenous ZnO domain-confined etching strategy provides a new insight into the exploration of advanced carbon anode. [ABSTRACT FROM AUTHOR]