The selective liquid-liquid extraction of Fe3+ cation from the aqueous phase to the organic phase was carried out by using p-tert-butylcalix[4]arene [L(1)], calix[4]arene [L(2)], p-nitro-calix[4]arene [L(3)], calix[4]arene p-sulfonic acid [L(4)], p- (diethylamino)methylcalix [4] arene [L(5)], tetramethyl-p-tert-butylcalix[4]arene tetraketone [L(6)], 25,27-dimethyl-26, 28-dihydroxy-p-tert-butylcalix[4]arene diketone [L(7)], calix[4] arene-bearing dioxime group on the lower rim [L(8)], and a monooxime [L(9)]. The effect of varying pH upon the extraction ability of calixarenes substituted with electron-donating and electron-withdrawing groups at their p-position was examined. Observed results were compared with those found for unsubstituted calix[4]arene.