The interface structure and the wetting behaviour in the B4C/(Me-Ti) (Me = Cu, Ag, Sn and An) systems were examined taking into account the solubility of boron in the melts and new phase formation at the interface. Wetting in the B4C/(Cu-Ti) system may be attributed to direct contact between TiB2, formed at the interface, and the Cu-Ti melt. The equilibrium contact angle in the B4C/Me-Ti systems, Me = Ag, An and Sn, reflects probably the formation of a non-stoichiometric TiCx surface layer with a carbon content determined by the activity of titanium in the corresponding melt. The experimental results are in good agreement with the results of a thermodynamic analysis of the B4C/Me-Ti systems. (c) 2004 Elsevier B.V. All rights reserved.