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The lubricating property of mold slag is significant to determine the surface quality of strands. To investigate the friction property of mold slag in the mold, the friction coefficient of the crystalline slag and glassy slag at high temperatures was measured through using a friction and wear testing machine. An edible oil was selected to simulate the lubrication behavior of liquid slag. The results show that during raising temperature from 25 °C, the friction coefficient of slag will increase due to the surface softening. The surface sintering will obviously reduce the friction coefficient of crystalline slag at around 800 °C. The friction coefficient of glassy slag is smaller than that of crystalline slag. The equivalent friction coefficient of liquid slag is below 0.2. The measured friction coefficient can be applied in mathematical models of friction.