The ex-solution phenomenon has received attention as a promising technique to prepare highly durable heterogeneous catalysts. Perovskite materials have been mainly used as host oxides for ex-solution, but their small surface areas have limited their practical use. Here, Rh was ex-solved by reducing Rh-doped ceria solid solution, and nanosized Rh catalysts with a high surface area of 70.7 m2/g were prepared. The Rh nanoparticles ex-solved from the ceria nanodomains were directly monitored by in situ transmission electron microscopy. The Rh nanoparticles whose sizes are 2-3 nm were not coarsened during the propane steam reforming process carried out at 700 °C for 65 h, leading to high resistance against sintering and coke formation. On the contrary, the Rh catalyst simply deposited on CeO2 was significantly sintered after the reaction, and the size of Rh nanoparticles increased to 25 nm, resulting in severe coke formation. Our work shows that ex-solution from a ceria-based nanodomain can be a good way to prepare metal nanoparticle catalysts with a large surface area and excellent durability for gas-phase reactions at high temperatures.