Investigation of benzene adsorption on different metal surfaces closer to a practical system appears to be avery important intermediate stage to utilize the conclusion obtained on single-crystal surfaces. In this paper, we studied the electrochemical adsorption behaviors of benzene on roughened Pt group electrodes usingsurface enhanced Raman spectroscopy (SERS). The effects of potential, surface roughness, and benzeneconcentration were investigated. Significant difference in surface Raman spectra of benzene on Ru, Rh, Pd,and Pt surfaces were found. On Pt surfaces, the parallel-chemisorbed benzene, the vertical dissociated chemisorbedbenzene, and the physisorbed benzene were observed, evidenced by the ring vibration mode appearingat 872, 1012, and 991cm-1, respectively. On Pd, only parallel-chemisorbed benzene and physisorbed benzenewere found. On Rh and Ru, the SERS signals were mainly from the parallel-chemisorbed benzene, with anextremely weak signal from the physisorbed benzene. The potential dependent study reveals that the parallelchemisorbedspecies interacts strongest with the substrate, while the physisorbed species can be easily removedat positive potentials. The models for the adsorbed benzene were given to account for the different types ofbenzene on these Pt group metals. The difference in the atomization heat of the four metals was used tointerpret the different interaction strength of benzene with Pt group metals.