Designing novel nanostructured materials is very significant to enhance the desalination capacity enabled by capacitive deionization (CDI). In this work, a vertically-aligned CuAl-layered double oxide grown on reduced graphene oxide (CuAl-LDO/rGO) is proposed as a high-performance anode for hybrid CDI (HCDI). It is found that the morphology of CuAl-LDO is ultimately dependent on the loading mass of urea. As a result, the optimized CuAl-LDO/rGO exhibits a relatively high specific surface area, 3D porous structure and electrochemical behavior. When employed as an anode for HCDI, it demonstrated a high salt removal capacity of 64.0 mg g⁻¹ at a cell voltage of 1.2 V in NaCl solution with an initial concentration of 1000 mg L⁻¹. After 20 cycles, the capacity still remains at 58.0 mg g⁻¹ which is ∼90% of the initial value, suggesting the superior cycling ability. Moreover, the phase transformation of CuAl-LDO/rGO at various stages indicates that the formation of Cu(OH,Cl)₂·2H₂O may be responsible for the capacity decay upon cycling. However, the morphology characterization realizes that the aggregation of Cu(OH,Cl)₂·2H₂O nanoparticles can be effectively inhibited within CuAl-LDO/rGO compared to that of randomly oriented CuAl-LDO nanoflakes, which accounts for the superior salt removal capacity retention. Besides, a comparison of HCDI performance is performed among different anodes, highlighting the advantages of CuAl-LDO/rGO. The good performance is attributed to the unique structure of CuAl-LDO/rGO as it provides many tunnels for diffusion of salt ions and active sites for intercalation.