The surface chemistry of S-2 and SO2 on Rh(111), Pd/Rh(111) and polycrystalline Pd has been investigated using synchrotron-based high-resolution photoemission and ab initio self-consistent-field calculations. Pd adatoms lead to an increase in the rate of adsorption of S-2 on Rh(111), but they are less reactive than atoms of pure metallic palladium: Rh(111) S-a + 2O(a)) or transforms into SO3/SO4 species. The molecular SOx species disappear upon annealing to 450 K and only atomic S and O remain on the surfaces. A Pd monolayer supported on Rh(111) is not very active for the dissociation of SO2. In this respect, the Pd-1.0/Rh(111) system is less chemically active than pure Pd or Rh(111). The electronic perturbations associated with the Pd-Rh bonds reduce the electron donor ability of Pd, weakening the interactions between the Pd 4d orbitals and the lowest unoccupied molecular orbitals of S-2 and SO2. The behavior of the S-2/Pd/Rh(111) and SO2/Pd/Rh(111) systems shows that bimetallic bonding can reduce the reactivity of Pd towards sulfur-containing molecules. A very large drop in reactivity can be expected when Pd is bonded to s,p or early transition metals.