Pb(Zr0.53Ti0.47)O-3(PZT) and PbNi1/3Nb2/3-PZT (PNN-PZT) multilayers with Ag/Pd 70/30 inner electrodes have been studied from the point of view of the ceramic-electrode interaction. PZT multilayers have shown silver free ceramic layers, and no lead has been detected in the electrode after sintering. Silver transport through the ceramic is avoided because of low open porosity-close porosity transition temperature. This transition seems to occur prior to the strong increase of the silver vapour pressure. For PNN-PZT multilayers, similar behaviour to that commonly reported in the literature for PZT is observed. A constant amount of silver, independent of the distance from the electrode, is detected in the ceramic layer. Lead is also detected in the electrode. On the other hand, no interaction between ceramic and electrode has been observed for the other cations.