Synchrotron X-ray computed nanotomography (nCT) and Focused Ion Beam-Scanning Electron Microscope nanotomography (FIB-nT) were used to characterize baked-out and sintered nickel (Ni) electrode-Multilayer Ceramic Capacitors. The three-dimensional microstructures obtained by two different tomography techniques were quantified and correlated. X-ray nCT is sufficient to reveal the pore characteristics, whereas the FIB-nT enables the particles in the initial packings to be identified. In the dielectric ceramic layers, pores preferentially orient horizontally in the layer and the regions near the Ni/BT interface are denser than the inner regions. This anisotropy is possibly caused by compressive stress induced during the heating stage.