The electrodes of a polymer electrolyte fuel cell (PEFC) are composite porous layers consisting of carbon and platinum nanoparticles and a polymer electrolyte binder. The proper composition and arrangement of these materials for fast reactant transport and high electrochemical activity is crucial to achieving high performance, long lifetimes, and low costs. Here, the microstructure of a PEFC electrode using nanometer-scale X-ray computed tomography (nano-CT) with a resolution of 50 nm is investigated. The nano-CT instrument obtains this resolution for the low-atomic-number catalyst support and binder using a combination of a Fresnel zone plate objective and Zernike phase contrast imaging. High-resolution, non-destructive imaging of the three-dimensional (3D) microstructures provides important new information on the size and form of the catalyst particle agglomerates and pore spaces. Transmission electron microscopy (TEM) and mercury intrusion porosimetry (MIP) is applied to evaluate the limits of the resolution and to verify the 3D reconstructions. The computational reconstructions and size distributions obtained with nano-CT can be used for evaluating electrode preparation, performing pore-scale simulations, and extracting effective morphological parameters for large-scale computational models.