Feasibility studies for the recovery of Pd(II) from leach liquors of automotive catalysts using p-diethylphosphonomethylthiacalix[6]arene (1) and p-tert-butylthiacalix[6]arene (2) were conducted. Compound 1 was found to be a more efficient extractant than 2 for Pd(II) ions, indicating selective extraction of Pd(II) ions [E% = 98.4%] from the leach liquors. The majority of other metal ions present in the leached solution were not extracted except Zr(IV) ions [E% = 22%]. Stripping of the Pd(II) ions from the extractants was performed using acidic thiourea, thereby enabling the recycling of the extractants.