Designing high-performance carbonous electrodes for capacitive deionization with remarkable salt adsorption capacity (SAC) and outstanding salt adsorption rate (SAR) is quite significant yet challenging for brackish water desalination. Herein, a unique gelation-assisted strategy is proposed to tailor two-dimensional B and N-enriched carbon nanosheets (BNCTs) for efficient desalination. During the synthesis process, boric acid and polyvinyl alcohol were cross-linked to form a gelation template for the carbon precursor (polyethyleneimine), which endows BNCTs with ultrathin thickness (∼2 nm) and ultrahigh heteroatoms doping level (14.5 atom % of B and 14.8 atom % of N) after freeze-drying and pyrolysis. The laminar B, N-doped carbon enables an excellent SAC of 42.5 mg g -1 and fast SAR of 4.25 mg g -1 min -1 in 500 mg L -1 NaCl solution, both of which are four times as much as those of activated carbon. Moreover, the density functional theory (DFT) calculation demonstrates that the dual doping of B and N atoms firmly enhances the adsorption capacity of Na + , leading to a prominent chemical SAC for brackish water. This work paves a new way to rationally integrate both conducive surface morphology and systematic effects of B, N doping to construct high-efficiency carbonaceous electrodes for desalination.