Isosteric heat of adsorption is exquisitely sensitive to structural changes in carbon surfaces based on the energetic behavior of the interactions between adsorbates and carbon materials. We discuss the relationships between porous structures, oxygen functional groups, and heat of adsorption based on the behavior of the heat of adsorption of polar and non-polar fluids on porous carbon materials with oxygen functional groups. The porosity and functional groups of porous carbon materials were estimated from N-2 adsorption isotherms at 77 K and temperature-programmed desorption. High-resolution adsorption isotherms of water, acetonitrile (polar fluid), and n-hexane (non-polar fluid) were measured on porous carbon materials with different pore size distributions and amounts of oxygen functional groups at various temperatures. The heats of adsorption were determined by applying the Clausius-Clapeyron equation to the adsorption isotherms. The heat of adsorption curves directly reflect the effects of interactions of fluid-oxygen functional groups, fluid-basal planes of pore walls, and fluid-fluid interfaces. In particular, the heat of adsorption curve of water is very sensitive to surface oxygen functional groups. This finding indicates the possibility of estimating the relative amounts of oxygen functional groups on porous carbon materials based on the amounts of water adsorbed at specific relative pressures. (C) 2019 Elsevier Inc. All rights reserved.