Abstract Xenon ion-bombardment used in conjunction with Auger electron spectroscopy was able to discriminate two types of carbonaceous materials accumulated on the surfaces of iron oxide and rhenium/iron-oxide catalysts spent for CO hydrogenation at 250°C and 2.1 MPa. One of the carbonaceous materials was easily eliminated from the surfaces by ion bombardment or by heat-treatment in vacuo at 150°C. On iron oxide only this “soft” carbonaceous material was present. On rhenium/iron oxide, bombardment-resistant “hard” carbonaceous material was also found. The presence of this hard carbonaceous material had little effect on the level of CO hydrogenation activity or the deactivation behavior of this catalytic system.