A number of organobentonites were synthesized by exchanging the metal ions in bentonite with the cationic surfactant, cetyltrimethylammonium bromide. Samples of natural bentonite and organobentonites were analyzed for their organic carbon contents, examined by X-ray diffraction (XRD) for interlayer spacings, and viewed using a scanning electron microscope (SEM) for surface morphology. The sorption isotherm of benzene vapor from ambient air (relative humidity (RH) = 45 ± 5%) on natural bentonite was nonlinear; however, the isotherms of benzene from ambient air onto organobentonites were virtually linear over a large range of relative vapor concentrations. The sorption capacities of air-dried organobentonites were far greater than that of the natural bentonite. For air-dried organobentonites, the sorption coefficients correlated positively with the sample organic carbon contents and negatively with the sample BET-N2 surface areas. The heats of benzene vapor sorption onto air-dried organobentonites were less exothermic than the heat of benzene-vapor condensation. These findings suggest that benzene vapor sorption by air-dried organobentonites occurs essentially by vapor partition into the sample organic-matter fractions. This offers a potential application of organobentonites for the removal of organic vapors from flue gases and for assessing the efficiency of vapor removal.