p-tert-Butylthiacalix[4]arene tetrathioesters 2a–c and tetrathioamides 4a–c in three different conformers (cone, partial cone and 1,3-alternate respectively) have been synthesized. The later were characterized by different physical methods IR, 1H NMR,13C NMR and X-ray crystallography. Their recognition abilities towards different alkali, earth alkaline and transition metals such as (Na?,K ?, Cs ?, Ba 2?, Pb 2?, Ag ?, Cd 2?, Hg 2? and Co2?) cations have been examined by metal picrate extraction from aqueous solutions into dichloromethane.