Interfacial oxidation–reduction reaction is herein developed to prepare hollow binary oxide nanostructures. Ce–Mn nanotubes are fabricated by treating Ce(OH)CO3 templates with KMnO4 aqueous solution, where MnO4− is reduced to manganese oxide and the Ce3+ in Ce(OH)CO3 is simultaneously oxidized to form cerium oxide, followed by selective wash with HNO3. The resulting Ce–Mn binary oxide nanotubes exhibit high catalytic activity towards CO oxidation and show significant adsorption capacity of Congo red. Moreover, guided by the same interfacial-reaction principle, binary oxide hollow nanostructures with different shapes and compositions are synthesized. Specifically, hollow Ce–Mn binary oxide cubes, and Co-Mn and Ce-Fe binary oxide hollow nanostructures are achieved by changing the shape of the Ce(OH)CO3 templates from rods to cubes, by changing the tempates from Ce(OH)CO3 nanorods to Co(CO3)0.35Cl0.20(OH)1.10 nanowires, and by replacing the oxidant of KMnO4 with another strong one, K2FeO4, respectively. This work is expected to open a new, simple avenue for the general synthesis of hollow binary oxide nanostructures.