Common methods in capacitive deionization (CDI) for selective removal are derived from membrane separation mechanism or size-based intercalation mechanism. In this study, based on the electrochemical activity of bismuth (Bi) material to chloride ions (Cl-) and inertness to sulfate ions (SO42-), Bi electrode is used as anode in CDI to selectively remove C-l- ions from mixed NaCl and Na2SO4 solution. Through the reaction with Bi, Cl- ions are stored in bismuth oxychloride (BiOCl). Results show that Bi electrode exhibits selectivity for Cl- over SO42- with a selectivity coefficient of more than 1.5 in solutions with mole ratio of Cl- to SO42- larger than 1. The selectivity coefficient is greatly dependent on the mole ratio of Cl- to SO42- and increases when the ratio rises. In solution with a fixed Cl-/SO42- mole ratio, higher applied voltage and prolonged time result in higher Cl- ion removal capacity, but not necessarily better selectivity. The highest selectivity coefficient of 4.5 is achieved in 8.5 mM NaCl and 1.1 mM Na2SO4 mixed solution at voltage of 1.6 and 2.0 V after charging for 1 h. These results demonstrate that Bi electrode can selectively remove Cl- ions from mixed solution with a relatively lower concentration of SO42- ions, which provides new insights into ion separation and selective removal by CDI.