Three series of heterocycle substituted calixarenes, derivatized at lower and upper rim, were synthesized and successfully evaluated for metal extraction towards alkali, alkaline, transition and heavy metal ions. The presence and placement of sulfur, heterocycle functionality at upper/lower rim played a crucial role toward the extractability and selectivity of metal ions. The lower rim substituted calixarenes have shown high extractability and poor selectivity. In contrast to this, upper rim substituted calixarenes exhibited good selectivity. Moreover, sulfur functionalized calixarenes have shown better selectivity for heavy metal ions than alkali and alkaline metal ions. Among upper rim substituted calixarenes, 17 and 18 were found to be suitable for Na+, K+ and Ag+, 19,13 for heavy metal ions i.e., Pb2+, Hg+, Hg2+ and Ag+, and 11,12 for Pb2+ and Ag+ only.