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To improve the surface friction characteristics of cemented carbide, a Cr coating was deposited on cemented carbide substrate with the multiple arc plating technique. The surface and cross-section micrographs, adhesion force and micro-hardness of the Cr-coated cemented carbide were tested. The anti-friction and anti-wear behaviors of cemented carbide with and without Cr coating were investigated via the sliding friction test against a WC/Co ball. The tribological properties of cemented carbide were examined using a scanning electron microscope and energy dispersive X-ray analysis. The test results showed that Cr-coated cemented carbide possessed good adhesion properties and lower hardness. The average coefficient of friction for Cr-coated cemented carbide was reduced by 10–20% compared with that of an uncoated one. The primary wear modes of the Cr-coated sample were delamination of coating, flaking and abrasion wear. It can be found that the preparation of a Cr coating is an effective way to enhance the friction and wear performance of traditional cemented carbide.