Cations as potassium and magnesium play an important role in maintaining the stability of Enhanced Biological Phosphorus Removal (EBPR) process. In this paper potassium, magnesium and calcium behaviour in EBPR treatment plants has been studied. An ASM2d model extension which takes into account the role of potassium and magnesium in the EBPR process has been developed. Finally, a simulation of the effect on P removal of a shortage of K and Mg was studied. The experimental results showed that K and Mg play an important role in the EBPR process being cotransported with P into and out of bacterial cells. It has been observed that calcium is not involved in P release and uptake. The values of the molar ratios K/P (0.28 mol K mol P(-1)) and Mg/P (0.36 mol Mg mol P(-1)) were obtained accomplishing the charge balance, with different K/Mg mass ratios and without phosphorus precipitation. Model predictions accurately reproduced experimental data. The simulations carried out showed the important effect of the K and Mg influent concentration for P removal efficiency. The results illustrate that the proposed ASM2d model extension must be considered in order to accurately simulate the phosphorus removal process.