The sodiation and desodiation of sodium (Na) into the Super-P carbon anode material were investigated using electrochemical analyses, high-resolution transmission electron microscopy (HRTEM), and neutron powder diffraction (NPD). In the sodiated Super-P carbon, sodium is stored both in the graphite interlayer space of carbon nano-particles and pores between the particles. Sodium metal clusters found in micro-pores between the carbon particles are responsible for the large irreversible capacity of the Super-P electrode. The graphite interlayer distance increases on sodiation from 3.57 Å to two distinct values of ∼3.84 and 4.41 Å. The mechanism of the process is discussed.