Abstract Hard carbon is a standard anode material for Na‐ion batteries. However, its low crystallinity and diverse microstructures make obtaining a full understanding of the sodium storage mechanism challenging. Here, the results of a systematic ex situ small and wide angle X‐ray scattering study of a series of nanostructured hard carbons, which reveal clear evidence of sodium storage in the graphene–graphene interlayers and nanopores, are presented. Particularly, an emergence of a broad peak around q ≈ 2.0–2.1 Å −1 in the low voltage region is suggested to be an indicator that sodium is densely confined in the nanopores. Thus, classical X‐ray scattering techniques are demonstrated to be effective in elucidating the overall reaction scheme of Na insertion into hard carbon.