The efficient uptake of phosphate from aqueous solutions was achieved on layered double hydroxides (LDHs)-based electrodes via capacitive desalination in our previous study. The current follow-up work was mainly carried out to study the influence of various experimental parameters on the capacitive removal of phosphate using LDHs/activated carbon (LDHs/AC) composite electrodes. A series of batch experiments were implemented to investigate the experimental factors, including Mg²⁺/Al³⁺ ratios (2, 3, and 4), trivalent metal cations (Al³⁺, Fe³⁺, Cr³⁺), initial solution pH (from 3 to 10), coexisting anions (NO₃⁻, Cl⁻, SO₄²⁻), and ion strengths, in capacitive deionization. The electrode materials before and after capacitive deionization were characterized to reinforce the analysis of the adsorption mechanisms by X-ray powder diffraction, scanning electron microscopy, energy dispersive X-ray, cyclic voltammetry, and electrochemical impedance spectroscopy. Results indicated that the Mg-Al LDHs/AC electrodes exhibited higher phosphate adsorption capacity (80.43 mg PO₄³⁻/g), more regular morphology, and higher degree of crystallinity than that of Mg-Fe LDHs/AC and Mg-Cr LDHs/AC. Increasing Mg²⁺/Al³⁺ ratios enhanced the adsorption capacity of phosphate. The uptake of phosphate by Mg-Al LDHs/AC under circumneutral pH and low ion strength reached the maximum level. Furthermore, the presence of coexisting anions lowered the adsorption capacity of phosphate mainly due to the occurrence of a compressed electrical double layer. Therefore, the influence of different experimental parameters on phosphate removal via capacitive deionization by Mg-Al LDHs/AC necessitates a systematic investigation to optimize the preparation conditions of LDHs-based electrodes and several important operating parameters.