Focused ion beam-scanning electron microscopy (FIB-SEM) and nano-scale X-ray computed tomography (nano-CT) have emerged as two popular nanotomography techniques for quantifying the 3-D microstructure of porous materials. The objective of this study is to assess the unique features and limitations of FIB-SEM and nano-CT in capturing the 3-D microstructure and structure-related transport properties of porous fuel cell materials. As a test case, a sample of a micro-porous layer used in polymer electrolyte fuel cells is analyzed to obtain 3-D microstructure datasets using these two nanotomography techniques. For quantitative comparison purposes, several key transport properties are determined for these two datasets, including the porosity, pore connectivity, tortuosity, structural diffusivity coefficient, and chord length (i.e., void size) distributions. The results obtained for both datasets are evaluated against each other and experimental data when available. Additionally, these two techniques are compared qualitatively in terms of the acquired images, image segmentation, and general systems operation. The particular advantages and disadvantages of both techniques are highlighted, along with suggestions for best practice. (C) 2013 Elsevier B.V. All rights reserved.