The recyclable metal nanoparticle catalysts, rhodium in aluminum oxyhydroxide [Rh/AlO(OH)] and iridium in aluminum oxyhydroxide [Ir/AlO(OH)], were simply prepared from readily available reagents. The catalysts showed high activities in the hydrogenation of various arenes and ketones under mild conditions. Selective hydrogenation was possible for bicyclic and tricyclic arenes in high yields. The catalysts were active at room temperature even with a hydrogen balloon. Also, the catalysts showed high turnover frequency (TOF) values under solventless conditions at 75 °C under 4 atm hydrogen pressure: ca. 1700 h−1 in the hydrogenation of benzene. Furthermore, Rh/AlO(OH) can be reused for at least 10 times without activity loss. The catalysts were characterized by the transmission electron microscopy (TEM), powder X-ray diffraction (XRD), inductively coupled plasma (ICP), energy dispersive X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption and hydrogen chemisorption experiments. The sizes of rhodium and iridium particles were estimated to be 3–4 nm and 2–3 nm, respectively. Aluminum oxyhydroxide nanofibers of these catalysts have surface areas of 500–600 m2 g−1.