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Wire rope has different degrees of surface wear under long-distance transmission conditions, which leads to performance degradation and greatly threatens its safety and reliability in service. In this paper, friction and wear tests between the transmission wire rope and sheave under different sliding velocities (from 0.8 m/s to 1.6 m/s) were carried out using a homemade test rig. The material of the steel wires was low carbon steel, and pulley material was ASTM A36 steel plate. The sliding friction coefficient (COF), friction temperature rise, wear characteristic parameters and wear mechanisms of the wire rope were analyzed. Additionally, the effect of different wear on the fracture behavior of the wire rope was investigated by a breaking tensile test. The results show that the average COF in the relatively stable stage decreased from approximately 0.58 to 0.51 with the increase of sliding velocity. The temperature rise of the wire rope increased rapidly with an increase of sliding velocity, from approximately 52.7 °C to 116.2 °C. The maximum wear width was the smallest when the sliding velocity was 1.2 m/s (approximately 1.5 mm). The surface wear was characterized by spalling, furrowing and plastic deformation, which are strongly affected by the sliding velocity. The wear mechanisms of the wire rope were mainly adhesive wear and abrasive wear. Surface wear changes the fracture morphology of the wire rope and accelerates its fracture speed.