The author analysed the stability of cellulose triacetate (CTA)- and poly(vinyl chloride) (PVC)-based polymer inclusion membranes (PIMs) containing bis(2-ethylhexyl) phosphoric acid (D2EHPA) as a carrier for chromium(III) separation from mixtures of Cr(III)/Cr(VI) ions. He also studied the influence of carrier (D2EHPA) concentration in PVC- and CTA-based PIMs on chromium(III) ion transport, at different initial concentrations of the Cr(III) ions. Based on the results, the optimum range of carrier concentration in both membranes guaranteeing the fastest process was found. Moreover, PIMs with D2EHPA as the carrier worked as selective barriers for Cr(VI) ions. However, in the case of CTA/PIM, the increase in Cr(VI) concentration above 0.005 mol/dm3 negatively influenced Cr(III) transport, which was caused by the degradation of the polymer matrix. The PVC/PIM was not influenced by the Cr(VI) ions, thus PVC was definitely a better polymer for the synthesis of PIM for the separation of Cr(III/VI) ions. It was also demonstrated that both membranes were not stable over a long process time. The results reported in this study suggest that the factor that determines the stability of PIMs with D2EHPA is the presence of water in the membrane and the formation of unstable micellar structures.