Friction and wear properties of a high Nb-containing TiAl alloy against WC-8Co, Si3N4, and GCr15 in an unlubricated contact were investigated under various friction and wear conditions. The counterface material plays a key role in the friction and wear properties of the high Nb-containing TiAl alloy. The Si3N4/TiAlNb pair had the highest average friction coefficient caused by the abrasive wear and adhesive wear. The applied temperature had a strong effect on the friction coefficient of the Si3N4/TiAlNb and GCr15/TiAlNb pair. The WC-8Co/TiAlNb pair has the stable average friction coefficient under various friction and wear conditions due to the abrasive wear.