A novel calix[4]arene derivative 2 with amino functional groups at the lower rim was first prepared via introduction of nitro functional groups and amination of the dinitro derivative of calix[4]arene.The optically active monomers were synthesized by dehydration of L-leucine(and L-isoleucine) and 3,3’,4,4’-benzophenonetetracarboxylic- 3,3’,4,4’-dianhydride(3) followed by reaction with thionyl chloride to form 5a and 5b.Two methods,polymerization under microwave irradiation and solution polymerization in CH_2Cl_2/TEA,were then employed to carry out the condensation polymerization of 2 with the optically active monomers 5a and 5b,respectively.The polymerization conditions affected the kind of resulting polymers,poly(amide-imide)s(PAIs) 6a and 6b and poly(ester-imide)s(PEIs) 6a’ and 6b’ were obtained selectively in good yields and moderate inherent viscosities.Sorption-extraction experiments were carried out using cram picrate extraction method and verified good binding ability of the resulting calixarene-based polymers towards silver,alkali metal and toxic heavy metal cations.Also thermogravimetric analysis indicated that the resulting PAIs and PEIs were thermally stable. A novel calix [4] arene derivative 2 with amino functional groups at the lower rim was first prepared via introduction of nitro functional groups and amination of the dinitro derivative of calix [4] arene. The optically active monomers were synthesized by dehydration of L- leucine (and L-isoleucine) and 3,3 ’, 4,4’-benzophenonetetracarboxylic-3,3’, 4,4’-dianhydride (3) followed by reaction with thionyl chloride to form 5a and 5b. Two methods, polymerization under microwave irradiation and solution polymerization in CH 2 Cl 2 / TEA, were then employed to carry out the condensation polymerization of 2 with the optically active monomers 5a and 5b, respectively. These polymerization conditions affected the kind of resulting polymers, poly (amide-imide) s (PAIs) 6a and 6b and poly (ester-imide) s (PEIs) 6a ’and 6b’ were obtained selectively in good yields and moderate inherent viscosities. Selection-extraction experiments were carried out using cram picrate extraction method and verified good binding ability of the res ulting calixarene-based polymers towards silver, alkali metal and toxic heavy metal cations. Al thermogram analysis showed that the resulting PAIs and PEIs were thermally stable.