In solid oxide fuel cells (SOFC) the redox reactions are supported by composite porous materials and, therefore, the electrochemical activity of an electrode is a direct function of its microstructure. Ni-YSZ (Yttria Stabilized Zirconia) is a common choice for the anode material in SOFC. Recently advances in tomographic techniques have enabled researchers to probe electrode microstructures providing unprecedented access to a wealth of microstructural information regarding the distribution of ionic, electronic and pore phases in three dimensions. In this paper nano-scale X-ray Computed Tomography (nCT) and Focused Ion Beam (FIB) techniques have been used to characterize microstructures from the same Ni-YSZ anode sample, 3D reconstruction from both techniques are presented and a quantitative and qualitative comparison is provided. An advanced technique for sample preparation for nCT is also presented. ©The Electrochemical Society.