A serious of calix[4]arene derivatives containing azo and imino group in the lower rim were synthesized by substitution and condensation reactions from p-tert-butylcalix[4]arene. The structures of products were characterized by IR, 1H NMR, 13 C NMR and elemental analysis. Their complexation behavior toward various metal ions was investigated by UV/vis spectroscopy. The results showed that 25,27-dihydroxy-26,28-bis{2-[2-(N-(4-phenylazo-1-naphthyl)iminomethyl)phenoxy]-ethoxy}-p-tert-butylcalix[4]arene(4c) cou...