Using a periodic slab-model density-functional approach we compared the decomposition of ethylene on the M(111) surfaces of the transition metals M=Pd, Pt, Rh, and Ni. The set of model reactions included four dehydrogenation steps and one final C–C bond breaking: C 2 H 4 (ethylene)→C 2 H 3 (vinyl)→C 2 H 2 (acetylene)→C 2 H (ethynyl)→C 2 (carbon dimer)→C+C. The dehydrogenation steps of ethylene and vinyl are more facile than those of acetylene and ethynyl. Dehydrogenation reactions occur easier, both kinetically and thermodynamically, on Ni(111) and Rh(111) than on Pd(111) and Pt(111). C 2 decomposition is an exothermic process on Pd(111), Pt(111), and Rh(111), whereas the formation of C 2 , a precursor of graphene and coke, is kinetically and thermodynamically most plausible on Ni(111). The calculated results reveal trends of the binding energies (BE) of the species on the four metals in the order BE(C 2 H 4 )<BE(C 2 H 2 )<BE(C 2 H 3 )<BE(C 2 H)<BE(C 2 )<BE(C). The binding energies of ethylene and vinyl are largest on Pt(111) while other species with a lower hydrogen content exhibit the largest BE values on the surfaces Rh(111) and Ni(111). We also explored the effect of coverage on the binding energies.