The partial oxidation of methane to synthesis gas over rhodium sponge has been investigated by admitting pulses of pure methane and pure oxygen as well as mixtures of methane and oxygen to rhodium sponge at temperatures from 873 to 1023 K. Moreover, pulses of oxygen followed by methane and vice versa as well as pulses of mixtures of methane and labelled oxygen were applied to study the role of chemisorbed oxygen and incorporated oxygen in the reaction mechanism. The decomposition of methane on reduced rhodium results in the formation of carbon and hydrogen adatoms. During the interaction of pure dioxygen with rhodium the catalyst is almost completely oxidized to Rh2O3. In addition to rhodium oxide, oxygen is also present in the form of chemisorbed oxygen species. During the simultaneous interaction of methane and dioxygen at a stoichiometric feed ratio and a temperature of 973 K only 0.4 wt% Rh2O3 is present. The chemisorbed oxygen species are completely desorbed after 2 s. A Mars-Van Krevelen mechanism is postulated : methane reduces the rhodium oxide, which is reoxidized by dioxygen. Synthesis gas is produced as primary product. Hydrogen is formed via the associative desorption of two hydrogen adatoms from reduced rhodium and the reaction between carbon adatoms and oxygen present as rhodium oxide results in the formation of carbon monoxide. The consecutive oxidation of CO and H-2 proceeds via both chemisorbed oxygen and oxygen present as rhodium oxide. Continuous flow experiments were performed to compare rhodium and platinum. When compared to platinum, rhodium shows a higher conversion to methane at a comparable temperature and also a higher selectivity to both CO and H-2, the difference for CO being most pronounced. The observed differences in methane conversion and selectivities for the two catalysts are ascribed to the higher activation energy for methane decomposition on platinum compared to rhodium. An additional explanation for the difference in H-2 selectivity could be the higher activation energy for OH formation on rhodium compared to platinum.