There have been several studies regarding the tribological behaviour of ceramics such as SiC and alumina mated against steels or self-mated. Nevertheless, only little is known about possible tribochemical reactions when ceramics are mated against steels. In the present study, ceramic pins made of SiC (EKasicF) or alumina (F99.7) respectively were tested under dry sliding conditions against different steel disc counter bodies using a pin-ondisc tribometer. The different ceramics showed significant differences in their tribological behaviour, i.e., coefficient of friction and wear amount. Especially, the SiC couples showed significant differences in the wear amounts while these were quite similar for the alumina couples. The wear behaviour of the SiC couples is discussed in more detail. A correlation between chromium content of the steel discs was found for the SiC couples. The surfaces of selected specimens were analysed by Auger-Electron-Spectroscopy (AES). Wear for the SiC couples was mainly attributed to tribochemical reactions as far as the steel disc was containing the alloying element chromium in considerable amount. Furthermore, a simple wear schematic is proposed.