In this study, a novel azocalix[4]arene derivative, 5,11,17-tris[(1-naphtyl)azo]-25,26,27,28-tetrahydroxycalix[4]arene (NAC4) bearing napthyl groups on the upper rim was synthesized. Its complexation behavior for alkali, alkaline-earth and various heavy metal ions (Li+, Na+, K+, Rb+, Cs+, Mg2+, Ca2+, Sr2+, Ba2+, Pb2+, Hg2+, Ni2+, Cd2+, Cu2+, Zn2+, Co2+, Fe2+, Cr3+, Ag+) was investigated by spectroscopic and voltammetric methods. This chemosensor exhibits decreased absorbance in the presence of Hg2+ and a unique absorbance quenching effect only for Cr3+. In addition, a new absorption band centered at 565 nm with the formation of the 1:1 host-guest complex (Cr3+-NAC4) was observed in the case of Cr3+, leading to an obvious color change from light orange to dark lilac. In voltammetric experiments, Cr3+ ions decreased voltammetric peaks of NAC4, whereas no significant changes occurred in the presence of the other metal ions. The Benesi-Hildebrand method was used to determine a logarithmic value of 3.76 for the association constant of the complex between Cr3+ and NAC4. (C) 2010 Elsevier Ltd. All rights reserved.