The article describes the syntheses and extraction properties of new alkylnitrile and alkylamino substituted calix[4]arene based copolymers. These compounds have been synthesized via nucleophilic substitution reactions involving 5,11,17,23-tetra-tert-butyl-25,27-bis(cyanomemoxy)-26,28- dihydroxycalix[4]arene (3), or 25,27-iw(cyanomethoxy)-26,28-dihydroxycalix[4] arene (4) with 1,5-dibromopentane and bisphenol-A, followed by their reduction with sodium borohydride in the presence of Cocl2̇6H2o. In addition an oligomer containing pendant calix[4]arene units with nitrile functionalities on its lower rim has been synthesized via nucleophilic reaction involving 5,11,17,23-tetra-tert-butyl-25,27-bis(cyanomethoxy)-26,28- dihydroxycalix[4]arene 3 with p-dibromoxylene. The extraction properties of polymers 5-9 toward the HCr2O7- anion are also reported. Due to the higher oxidative stability of nitrile groups, polymers 5-7 have been developed as good extradants for transferring the HCr 2O7- anion from an aqueous into a dichloromethane phase.