Friction and wear of tribopairs: 6%(TiC + TiB)/TC4 composite sliding against Cr12MoV and GCr15 steels were conducted under the load of 150–300 N at 0.22, 0.55, 1.10 m s−1, respectively. For two kinds of counterface materials, the wear behavior of composite varied with different friction conditions. The remarkable variations in wear properties of composite were due to the existence of tribo-layers, a compact and stable tribo-layer was formed on the worn surface at 0.55 m s−1, while at 1.10 m s−1, the unstable tribo-layer was easy to fall off, thus leading to the rise of specific wear rate. Through the comparison to the effect of two counterface steels, the tribo-pair of composite sliding against GCr15 steel possessed better wear resistance.