We have performed a near-edge X-ray absorption fine-structure (NEXAFS) and a transmission electron microscopy (TEM) investigation of freely suspended graphene oxide (GO) sheets. We utilized a photoemission electron microscope to identify GO membranes and to acquire C K and 0 K absorption spectra. The overall line shape of C K-edge spectra demonstrates that the honeycomb carbon network of graphene is the scaffold of GO. However, the intensity ratio of pi* and sigma* resonances, and a broad feature at about 20 eV from the edge, indicate the presence of new carbon bonds. The 0 K-edge spectra show that oxidized regions are made of carbonyl, epoxide, and hydroxyl groups attached to the plane of graphene, while carboxyl groups might also be present at the edges. Further, our study indicates the presence of ordered arrangements of oxygen atoms in GO sheets. Our investigation provides a new and efficient route to study the electronic structure of suspended membranes. (C) 2010 Elsevier Ltd. All rights reserved.