Thermal gravimetric analysis (TGA) and differential thermal analysis (DTA) involving air oxidation of fluid coke, coal-tar pitch delayed coke and needle coke suggested that active sites are present which can be correlated to the crystallographic parameters, L a and L c , and the d(002) spacing. This finding was extended to determine the relationship between active sites on carbon and their role in catalyzing electrolyte decomposition leading to irreversible capacity loss (ICL) in Li-ion batteries. Electrochemical data from this study with graphitizable carbons and from published literature were analyzed to determine the relationship between the physical properties of carbon and the ICL during the first charge/discharge cycle. Based on this analysis, we conclude that the active surface area, and not the total BET surface area, has an influence on the ICL of carbons for Li-ion batteries. This conclusion suggests that the carbon surface structure plays a significant role in catalyzing electrolyte decomposition.