This study investigated the efficacy of oxidised iron-loaded activated carbon cloth (Fe-ACC) for selective recovery of phosphorous. The capacitive deionisation (CDI) technology was employed, for rapid removal of phosphate, with the aim of reducing the reliance on high alkalinity environment for the regeneration of Fe-ACC electrode. Multiple experimental parameters, including applied potential, pH, and co-existing ions, were studied. Additionally, the CDI system was tested on a real water matrix (Lake Ormstrup, Denmark) to elucidate the electrodes’ performance on selective recovery of phosphate. About 69 ± 10% of the adsorbed phosphate were released at pH 12 via pure chemical desorption, which was ~ 50% higher than that at pH 9. The CDI system successfully demonstrated the selective removal of phosphate from the lake water. It reduced the concentration of phosphate from 1.69 to 0.49 mg/L with a 71% removal efficiency, while the removal percentages of other anions, namely chloride, sulphate, bromide, nitrite, nitrate, and fluoride, were 10%, 7%, 1%, 1.5%, 4%, and 7%, respectively.