Herein, the edges in carbon materials were quantitatively evaluated by summing the amount of hydrogen and the amount of functional groups without hydrogen in the material. The amount of hydrogen in the carbon material was quantitated via temperature-programmed oxidation (TPO) under an oxygen atmosphere, whereas the amount of functional groups was determined via temperature-programmed desorption (TPD) of the sample under an inert atmosphere. Consequently, the amount of edges in exfoliated carbon fibers prepared from polyacrylonitrile (PAN) (referred to as PAN-1000) was 9.4 mmol g−1. In addition, Ketjen Black (KB) and activated carbon (AC) had edge content of 1.3 and 3.6 mmol g−1, respectively. Because the total amount of functional groups of PAN-1000, KB and AC were estimated to be 8.18, 0.082 and 1.02 mmol g−1 via TPD, the total amount of edges and oxygen-containing functional groups of each sample could be quantified. The difference between amount of edges and the amount of functional groups is speculated to correspond to the amount of edges terminated with hydrogen. This study revealed that detailed information about the edges such as their proportion terminated with oxygen-containing functional groups, the species and amount of oxygen-containing functional groups via a combination of TPO and TPD.