We demonstrate that near-edge X-ray-absorption fine-structure spectroscopy combined with full-field transmission X-ray microscopy can be used to study the electronic structure of suspended carbon nanohorns. Based on reports of electronic structure calculations additional spectral features observed in the 蟺 region of the NEXAFS spectrum recorded on the carbon nanohorns were associated to the presence of the pentagonal rings and the folding of the graphene sheet.