It is the first report to observe the real-time behavior of photodeposition and the continuous structural change of Rh metal particles anchored on a TiO(2) photocatalyst from an aqueous solution of Rh trivalent ions in the liquid-solid suspension by an in situ time-resolved energy-dispersive X-ray absorption fine structure (DXAFS) analysis. The DXAFS analysis uncovered that the Rh trivalent ions are adsorbed on the surface of the TiO(2) photocatalyst, followed by reducing to the Rh metal particles by acceptance of electrons because the coordination number of a Rh-Rh bond evaluated by the Fourier transforms of EXAFS spectra and the amount of the Rh trivalent ions determined by the ICP analysis linearly increased and decreased with elongation of photoirradiation time, respectively. The generation rates of the Rh metal particles and the diminution rates of the Rh trivalent ions depended on the type of sacrificial reagents and tends to become slower in the order corresponding to methanol > ethanol >> 1-propanol > 2-propanol. The coordination number of a Rh-Rh bond stopped increasing after 90 min of photoirradiation in the case of methanol. The coordination number was evaluated to 10, although that of Rh foil is 12, suggesting the generation of Ultrafine Rh particles on TiO(2).