Novel micrometer-sized indium oxyhydroxide (InOOH) hollow spheres were successfully synthesized via a citric acid (CA) assisted hydrothermal process. The morphology, crystal structure, and optical properties of the product were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, and UV-vis diffuse reflectance spectroscopy (DRS). The optical band gap, E(g), was estimated to be 3.5 eV from the DRS spectrum, which is almost equal to that of indium oxide. Furthermore, on the basis of a series of SEM observations, phenomenological elucidation of a mechanism for the growth of the InOOH hollow spheres has been presented; key factors for the formation of the structures have been proposed.