The study of the contact characteristics between functional ceramics and potential electrode metals is of primary importance when developing new devices. BaTiO3 is the most used dielectric ceramic and its functional properties are tailored by the introduction of substituents. In this work, we verify the effect of the zirconium substituents in BaTi1−xZrxO3 (x = 0, 0.1, 0.2, 0.4) ferroelectric perovskites on the wettability by liquid Ag and Ag-3 at% Cu alloy at 1000 °C in air, and the obtained metal/ceramic interfaces are characterised.With x going from 0 to 0.4, the contact angles increase from 83° to 104° and from 46° to 72° for pure Ag and Ag-3 at% Cu respectively. This trend is in agreement with the increased band-gap energy of the perovskites ascribed to the increase of Zr content. The better wetting of Ag-3 at% Cu compared to pure Ag is due to the formation of interfacial CuO; no further interfacial phenomena nor mutual interdiffusion are detected.