Investigations of the electronic structure of graphene nanosheets synthesized by the reduction of oxidized graphene nanosheets were carried out using ultra-soft X-ray emission spectroscopy (USXES). Oxidized graphene nanosheets were produced from carbon nanofiber starting material using a modified Hummers method. X-ray diffraction, and scanning and transmission electron microscopy investigations were used in addition to USXES to study the electronic structure evolution from carbon nanofibers to graphene nanosheets. The effect of the degree of corrugation of the graphene nanosheets on the fine structure of the CK(alpha)-emission bands was revealed by USXES. It was found that corrugation of the graphene nanosheets is caused by overlapping of the pi-orbitals and formation of mixed (sigma + pi)-states.