The adsorption of benzene on Rh(lll) was investigated by using low-energy electron diffraction (LEED), thermal desorption spectroscopy (TDS), and angle-resolved ultraviolet photoelectron spectroscopy (ARUPS).Under very good vacuum conditions we found a (\/l9 x \/l9)R23.4°pure benzene adsorption structure which could be converted to the c(2- = -1.47 eV, indicating one of the highest benzene densities on Rh(l 11) observed so far. A considerable dispersion of the 2aig-derived band of the adsorbate layer was observed.