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Amutiphase model of metal ion speciation in human interstitial fluid was constructed and the effect of Pr(III) on Ca(II) speciation was studied. Results show that Ca(II) mainly distributes in free Ca2+, [Ca(HCO3)], and [Ca(Lac)]. Because of the competition of Pr(III) for ligands with Ca(II), with the total concentration of Pr(III) rising, the percentages of free Ca2+, [Ca(Lac)] and [Ca(His)(Thr) H3], gradually increase and the percentages of CaHPO4(aq) and [Ca(Cit)(His) H2] gradually decrease. However, the percentages of [Ca(HCO3)] and CaCO3(aq) first increase, and then begin to decrease when the total concentration of Pr(III) exceeds 6.070μ10–4 M.