The possible configurations of benzene and pyridine molecules adsorbed in microporous carbon were analyzed by synchrotron radiation-excited soft X-ray emission spectroscopy and by analyzing its spectral features using DV-XQ molecular orbital calculations. The distances between the adsorbed molecules and the graphitic surface were estimated to be approximately 0.33 nm in both benzene- and pyridine-adsorbed systems. Both molecular orientations were also estimated to be almost parallel to the graphitic surface of microporous carbon. The electronic states of benzene and pyridine molecules adsorbed on the graphitic surface were similar to those of individual nonadsorbed free molecules. Therefore, the adsorption of benzene and pyridine molecules in the microporous carbon can be confirmed to be physisorption, and there is little charge-transfer between the adsorbed molecules and the graphitic surface.