A series of upper-rim p-allyl and p-methoxyphenylazocalixarenes (6, 8, 9a,b, and 10a,b) were synthesized and shown to exhibit substantial color changes upon complexation with Hg2+ ion. Both the upper-rim p-allyl- and p-methoxyphenylazo groups on calixarenes are proven to be key components in the recognition of Hg2+ ion. Job's plots revealed 1:1 binding stoichiometry for all these p-allyl- and p-arylazo-coupled calixarenes with Hg2+ ions and Benesi-Hilderbrand plots were used for determination of their association constants. Our results also demonstrated that two p-methoxyphenylazo groups prefer to bind Hg2+ in a distal orientation rather than a proximal one, and if there are three p-methoxyphenylazo groups, the third flanking p-methoxyphenylazo group plays a role in disturbing the binding of the two distal diazo groups. Furthermore, it should be noted that triazocalixarenes (6, 9a, and 9b) responded to all 14 metal ions without showing much preference among the eight transition-metal ions screened in this work (Cr3+, Ni2+, Cu2+, Ag+, Cd 2+, Hg+, Hg2+, and Pb2+).