Three new thiacalix [4] arene derivatives, 5,11,17,23-tetra-tert-butyl-25,27-di (2-hydroxyethoxy)-26,28-dihydroxythiacalix-[4] arene (2), 5,11,17,23-tetra-tert-25, 26,27,28-tetrakis [(methylcarboxyl)methoxy] thiacalix [4] arene (3), 5,11,17,23-tetratert-butyl-25,26,27,28-tetrakis(2-hydroxy-1-propanoxy)thiacalix [4] arene (4), were synthesized for the first time. The coordination properties of thiacalix [4] arene (1) and its derivatives (2and4) were investigated by detecting the interactions between these compounds and two palladium complexes, cis-[Pd(en)(H2O)2]2+ and cis-[Pd(dtco-3-OH)(H2O)2]2+, by means of electrospray ionization mass spectrometry (ESI-MS) technique.