While an increasing amount of data is becoming available on the sorption capacity of natural coals for pure CH4 and CO2 at different temperatures and pressure ranges, only few measurements have been reported for mixtures of two or more gas components under the conditions of competitive sorption. High-pressure adsorption/desorption experiments with CO2/CH4 gas mixtures have been carried out on 10 coals of different rank and composition to investigate their selectivity with respect to the sorption of the two gases. The sample set comprised two coals from the Netherlands, ranging in vitrinite reflectance from 1.19% to 1.56% VRD three coals from the Silesian Basin in Poland (VRr 0.68% to 0.78%) and five coals from the Argonne Premium Coal Sample Programme (VRr 0.25% to 1.68%). The experiments were performed in the dry and moisture-equilibrated state. In addition, the effect of grain size on the competitive sorption was examined. The results are reported as a guideline for predicting adequate coal properties with respect to CO2 injection and CO2 enhanced coal bed methane (ECBM) projects in the future. The volumetric sorption experiments were performed with a sequential arrangement of calibrated reference and measuring cells and a sample loop for transfer of gas samples to an on-line gas-chromatograph. The experiments were carried out at 45 degrees C and pressures up to 23 MPa. Only few measurements showed preferential adsorption of CO2 and preferential desorption of CH4, as commonly expected. Distinct variations were observed in the competitive adsorption and desorption behaviour of the different dry and moist samples, ranging from preferential adsorption of CH4 in the low pressure range to preferential desorption of CO2 over the entire pressure range. The observed preferential sorption phenomena give rise to the assumption that CO2 sequestration in coal seams with subsequent CO2-enhanced CBM production might only be an option in specific coal basins. (c) 2005 Elsevier B.V. All rights reserved.