The wetting of Cu-Fe two-phase composites by molten Sn is studied by the sessile drop technique under high vacuum at 400 degrees C. In this system Sn reacts with both solid components, forming intermetallic compounds. It is found that the curve of contact angle vs. the surface fraction of components passes through a minimum, behaviour that cannot be interpreted by existing models describing wetting of heterogeneous surfaces and/or reactive wetting. It is shown that the observed enhanced wetting can be explained by the dissolution contrast of Cu and Fe phases, leading to interfacial microroughness, thus providing an additional driving force for wetting. In order to take into account this new effect of interfacial reactions on wettability, an equation similar to Wenzel's equation is established. It is shown that this equation can explain the change in wettability of composites when Sn is replaced by SnPb eutectic presenting a lower reactivity than pure Sn, as well as the effect on wettability observed when the scale of composite microstructure is changed with the surface fraction of components remaining constant. (C) 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.