Calixarene carboxylate derivatives were used as a mobile carrier for rare earth permeation in a liquid surfactant membrane (LSM) system. The effect of alkali metal ions on the extraction behavior of rare earth metals in both liquid-liquid extraction and LSM systems has been studied. The addition of sodium ions considerably enhanced the extraction ability of rare earth metals in the extraction equilibrium. Furthermore, the presence of alkali metal ions in the material solution affected the rate of rare earth permeation in LSMs. The most accelerative transport of rare earth metals by LSMs was achieved by the addition of sodium ions. This acceleration effect of sodium ions was predominant in a tetracarboxylate calixarene whose cavity size just fits the ionic diameter of sodium ions. The sodium-loaded calix[4]arene derivative showed good performance as an effective mobile carrier for rare earth metals in the presence of sodium ions.