We synthesized hollow AuCu bimetallic nanostructures using a Cu2O template and evaluated their hydrogen dissociation performance. The formation of a superstructural bimetallic and well-inherited shape was confirmed using transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The AuCu bimetallic nanostructures were tested for the catalytic reduction of o-nitroaniline to 1,2-benzenediamine, and they showed much better catalytic activity than pure Au. The hollow AuCu cubic structure exhibited superior catalytic efficiency (reaction rate constant = 0.33 min(-1)) compared with other structures such as a cuboctahedral structure (0.08 min(-1)), an octahedral structure (0.17 min(-1)), and pure Au (0.06 min(-1)). Furthermore, we examined the dependence of o-nitroaniline reduction activity of the hollow AuCu hybrids on NaBH4 concentration. The reaction rate constant became saturated at a lower NaBH4 concentration for Au nanoparticles, while its saturation occurred at a higher NaBH4 concentration in the case of hollow AuCu nanostructures. (C) 2015 Elsevier Inc. All rights reserved.