Membrane capacitive deionization (MCDI) is an emerging technology for effective removal of charged pollutants from the water sources including domestic wastewater. In this work, a lab-scale MCDI system was employed to investigate its feasibility for effective phosphorus removal from domestic wastewater. The effect of phosphate equilibrium reactions on the ion sorption behaviour was studied in sodium phosphate buffer solution at typical pH range maintained in a real domestic raw wastewater effluent (between 6.5 and 8.5). The results demonstrated that phosphate equilibrium system has positive impact on the degree of inorganic phosphorus (P) adsorption capacity in aqueous solution. In addition, the ion selectivity of P over other co-existing anions (Cl-, SO42-) were experimentally studied using a synthetic wastewater solution. And it was found that the preferential electrosorption sequence of the competitive anions is: Cl- > SO42- > P, while the initial ion concentration order in the synthetic feed solution is: Cl- (1.90 mM) > P (0.40 mM) > SO42-(0.32 mM). The experiments with diverse operating conditions revealed that the optimal adsorption of inorganic phosphorus over chloride and sulphate can be achieved in some extent with slower flow rates and higher applied potentials (less than 1.23 V). (C) 2019 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.