The article describes the fabrication and characterization of a new 25,27-bis[5-(trimethyl ammonium bromide)pentyloxyl]-26,28-dihydroxyl-5,11,17,23-tetra-tert-butylcalix[4]arene-embedded polymer inclusion membranes (TMAC[4]Bu t @PI membrane). TGA, SEM and DSC techniques were performed to determine its structures. Moreover, the anion transport capacity of TMAC[4]Bu t @PI membrane against Cr(VI) anion was investigated.