Oxidation of the Al 9 Co 2 (0 0 1) and Al 13 Co 4 (1 0 0) surfaces has been performed in a wide range of temperatures at 2 × 10 -8 or 1 × 10 -7 mbar oxygen pressure. Only Al-O bonding is observed. The oxidation kinetics are controlled by the quantity of oxygen sticking on the surface. Oxidation results from a competition between several effects: formation of an oxide film, dissolution of the film, oxygen desorption and oxygen dissolution into the bulk. For temperatures lower than 710 K for the Al 9 Co 2 (0 0 1) surface and 925 K for the Al 13 Co 4 (1 0 0) surface, a ∼5 Å thick oxide film is formed which does not show any long-range order and desorbs upon annealing. When oxidation is performed at higher temperatures, oxygen diffusion into the bulk is observed. A poorly ordered oxide film having a sixton structure is formed on the Al 9 Co 2 (0 0 1) surface when oxidation is performed at 775 K, which is dissolved when annealing at higher temperatures. On the Al 13 Co 4 (1 0 0) surface, only a weak streaky polar circle is observed following annealing at 925 K the film formed at room temperature, which corresponds to an hexagonal network of O atoms into small ultrathin oxide layers domains. The oxidation behaviour of the Al 9 Co 2 (0 0 1) and Al 13 Co 4 (1 0 0) surfaces has been ascribed to the strong covalent character of bonds present in these Al-Co phases, which prevents aluminium diffusion. C 2 H n molecules (n = 2, 4, 6) do not adsorb on the Al 13 Co 4 (1 0 0) surface in the experimental conditions used in this study, thus suggesting that this surface might not be the active one in the semi-hydrogenation of acetylene.