The molecular recognition of tetra (p-t-butyl) tetrathiocalix [4] arene (I) and its three derivatives to heavy metal ions has been investigated by UV spectroscopy and solvent extraction. These erivatives include 5, 11, 17, 23,-tetra-t-butyl-25, 26, 27, 28-tetrakis (acetylmethoxy) tetrathiocalix [4] arene (II), 5, 11, 17,23-tetra-t-butyl-25, 26, 27, 28-tetrakis (2'-hydroxypropyloxy) tetrathiocalix [4] arene (III), 5, 11, 17, 23,-tetra-t-butyl-25, 27-bis (3'-hydroxy propyloxy) tetrathiocalix [4] arene (IV). The UV spectra and solvent extraction of I show that it has an effective molecular recognition to heavy metal ions, especially to Cd2, while IV has a special molecular recognition to Agion. These results confirmed the feasibilities for I to be applied in separation for toxic heavy metal ions Pb2, Cd2 and IV to be used as the sensor compound of Ag ion-selective electrode.