A combination of in situ time-resolved DXAFS and ICP-MS techniques reveals that the formation process of Rh nanoparticles (NPs) from rhodium trichloride trihydrate (RhCl(3)·3H(2)O) in ethylene glycol with polyvinylpyrrolidone (PVP) at elevated temperature is a first-order reaction, which indicates that uniform size Rh NPs appear consecutively and these Rh NPs do not aggregate with each other.