Effects of reduction temperature and phosphorus loading on rhodium phosphide (Rh2P) formation and on the catalytic activity of Rh-xP catalysts for hydrodesulfurization (HDS) were investigated to prepare highly active HDS catalysts. Analysis of the Rh-xP catalysts showed that a suitable P loading for HDS activity is 1.5 wt%—four times greater than that of an Rh catalyst. Temperature-programmed reduction and X-ray diffraction analyses of the Rh-xP catalysts showed that Rh2P is readily formed in catalysts with higher P loading. In contrast, the results of transmission electron microscopy observation and CO adsorption experiments indicated that the Rh2P particle size increased with increasing P content. Thus, the high HDS activity of the Rh-1.5P catalyst was explained by the formation of small Rh2P at a relatively low reduction temperature (550 °C