Several tetrahomodioxacalix[6]arene hexaesters, hexaacid and hexaamide derivatives were synthesized from tetrahomodioxacalix[6]arene by etherification with ethyl bromoacetate. It was found that p-tert-butyltetrahomodioxacalix[6]arene hexaethylester exhibited high selectivity towards lithium ion. p-tert-Butyltetrahomodioxacalix[6]arene hexaamides showed high ion-binding ability towards transition metal ions.