An unprecedented octahedral {Cd(30)} nanocage supported by twelve pendant-armed tetraacetate macrocyclic ligands was synthesized through the reaction of macrocyclic tetraethyl ester and Cd(OAc)(2)·2H(2)O in a 1 : 2 stoichiometry, where the surface photovoltage and photoluminescent properties have been studied for the nanocage.