1,3-Dipropyloxycalix[4]arene crown ether (CCE1) and 1,3-dipropyloxycalix[4]arene dibenzo crown ether (CCE2) were successfully synthesized in a fixed 1,3-alternate conformation with good yields by the reaction of corresponding 1,3-dipropyloxycalix[4]arenes with pentaethylene glycol ditosylate and dibenzodimesylate, respectively in the presence of cesium carbonate as a base. Solvent extraction of cesium picrates and cesium nitrate from aqueous solutions into chloroform by CCE1 and CCE2 were investigated. D-M value of calix[4]arene crown ether was 30-240 times of that of general crown ether and D-M value of CCE2 was almost eight times of that of CCE1. Through permeation experiments using thin sheet supported liquid membranes (SLM), the effect of operating variables on permeation coefficients were obtained. Permeation coefficient of cesium ion in case of using CCE1 as extractant was higher than that of using CCE2. Published by Elsevier Science B.V.