Using capacitive deionization to remove heavy metal ions from water has received much attention, but the inferior salt adsorption capacity (SAC) of electrode materials has always limited its practical application. Herein, N, S co-doped two-dimensional (2D) porous glucose derived carbon nanosheets (NSPGC) was successfully fabricated, utilizing the gas exfoliation by calcination of thiourea. The NSPGC demonstrates distinct 2D lamellas, high specific surface area (2529 m2 g-1), hierarchical pore structure and high wettability. In electrochemical tests, a high specific capacitance (127 F g-1) and electrons/ions transport performance can be achieved in the NSPGC, moreover it showed a prominent SAC of 206.57 mg g-1 and recoverability in 100 mg L-1 CuSO4 solution. Moreover, the density functional theory (DFT) calculation manifested the intrinsic affinity of Cu2+ improved by N, S co-doping, which played an essential role in enhancing the Cu2+ removal performance of CDI. Our work provided a new insight into the preparation of high-performance CDI electrode materials for Cu2+ removal and promoted the application of CDI in heavy metal wastewater.