High-chromium white cast iron (WCI) specimens locally reinforced with WC–metal matrix composites were produced via an ex situ technique: powder mixtures of WC and Fe cold-pressed in a pre-form were inserted in the mold cavity before pouring the base metal. The microstructure of the resulting reinforcement is a matrix of martensite (α’) and austenite (γ) with WC particles evenly distributed and (Fe,W,Cr)6C carbides that are formed from the reaction between the molten metal and the inserted pre-form. The (Fe,W,Cr)6C precipitation leads to the hypoeutectic solidification of the matrix and the final microstructure consists of martensite, formed from primary austenite during cooling and eutectic constituent with (Fe,Cr)7C3 and (Fe,W,Cr)6C carbides. The presence of a reaction zone with 200 µm of thickness, between the base metal and the composite should guarantee a strong bonding between these two zones.