An extraction and simultaneous back-extraction process with two hollow-fiber membrane contactors is evaluated for the continuous recovery of alkali metals and 1,3 bis-benzo-crown-6-calix[4]arene. The results show that this configuration operates as a “liquid membrane” (permeable only with alkali picrate) and order of the recovery yields is in agreement with the Donnan equilibrium. It is higher for the rubidium (75.8%) than for the cesium (68.1%) while it is only 11% for the potassium. This is a case where the high affinity of cesium picrate for the 1,3 bis-benzo-crown-6-calix[4]arene cannot be neglected and, as a consequence, its release in the back-extraction aqueous phase is more difficult. The effect of the alkali metal and the initial concentration on the system behavior shows that the concentration gradient controls the mass transfer. The kinetics are similar for the cesium and the rubidium whereas the mass-transfer resistance increases for the potassium. A high mass transfer in the first module can slow down the global-transport kinetics.