Calix[4]arene derivatives have been reported to possess high selectivity for metal ions.In order to analyze the extraction effect of substituents on Hg~(2+)and Pb~(2+),calix[4]arene derivatives containing hydroxyl,bromoethoxy and 1,11-dioxa-4,8-dithiahendecene were successfully synthesized,with their extraction effectiveness towards Hg~(2+)and Pb~(2+)were evaluated respectively.The results indicated that the phenolic hydroxyl in calix[4]arene improved the extraction ability on Hg~(2+)by promoting the formation of the negative oxygen ions that could bind with Hg~(2+)by coordination and ionic bonds.The extraction ability of 5,17-dinitro-26,28-(1’,11’-dioxa-4’,8’-dithiahendecene)-calix[4]arene(calix[4]arene thia derivative)was improved slightly due to the better coordination capacity for metal ions after introduction of 1,11-dioxa-4,8-dithiahendecene,which was a chelate-binding centre.Regarding to Pb~(2+),only 1,11-dioxa-4,8-dithiahendecene on molecule contributed to extraction due to the coordination bond.Since the metal ion with higher charge-to-radius ratio could coordinate with one ligand more stably,Pb~(2+)with higher charge-to-radius ratio than Hg~(2+)was coordinated and extracted by the calix[4]arene thia derivative more easily.Furthermore,extraction rates of the calix[4]arene thia derivative on both ions(Hg~(2+)and Pb~(2+))increased with the increase of pH value in acidic aqueous system(pH<7). Calix [4] arene reported have possess high selectivity for metal ions. In order to analyze the extraction effect of substituents on Hg ~ (2+) and Pb ~ (2 +), calix [4] arene derivatives containing hydroxyl, bromoethoxy and 1,11-dioxa-4,8-dithiahendecene were successfully synthesized, with their extraction effectiveness towards Hg 2+ and Pb 2+; respectively. These results indicate that the phenolic hydroxyl in calix [4 ] arene improved the extraction ability on Hg ~ (2+) by promoting the formation of the negative oxygen ions that could bind with Hg ~ (2+) by coordination and ionic bonds.The extraction ability of 5,17-dinitro-26, The calix [4] arene thia derivative was was able to improve slightly due to the better coordination capacity for metal ions after introduction of 1 (1 ’, 11’-dioxa-4’, 8’-dithiahendecene) , 11-dioxa-4,8-dithiahendecene, which was a chelate-binding centre.Regarding to Pb ~ (2 +), only 1,11-dioxa-4,8-dithiahendecene on molecule contributed to extraction du e to the coordination bond. Since the metal ion with higher charge-to-radius ratio could coordinate with one ligand more stably, Pb 2+ with higher charge-to-radius ratio than Hg 2+ was coordinated and extraction by the calix [4] arene thia derivative more easily. More than, extraction rates of the calix [4] arene thia derivative on both ions (Hg 2+ and Pb 2+) increased with the increase of pH value in acidic aqueous system (pH <7).