X-ray photoelectron spectroscopy (XPS) is among the most powerful methods to determine the surface chemical properties of carbon materials. Because heat-treated graphite oxide includes various defects, analyses of the structure by XPS help us understand the structures of various carbon materials. Thus, XPS spectra of graphene-related materials containing various functional groups and other defects on edges and in the basal plane were simulated and full width at half maximums (FWHMs) and peak shifts were obtained by density functional theory calculation. Shifts of whole C1s spectra were influenced by the electron-withdrawing functional groups such as C=O-containing functional groups. FWHMs of the main peak of C1s spectra were influenced by mainly electron-withdrawing functional groups in addition to defects such as vacancy, pentagons, and heptagons. Analyses using only XPS provide us limited information, even though the peak tops and FHWMs of simulated XPS spectra are used for assignment. Combination use of peak shifts and FWHMs of XPS spectra, infrared spectroscopy, and density functional theory calculation provided more reliable assignments of defects including oxygen-containing functional groups of carbon materials than commonly used methods using only peak shifts of XPS spectra.