Display omitted •Chemically reduced graphene oxide aerogels (rGOAs) for gas-phase separations.•Good selectivity of benzene/cyclohexane separation in the rGOAs.•Shape and size exclusion of cyclohexane from the rGOAs surface.•Kinetics and thermodynamics entangled in the hydrocarbons separation on rGOAs.•Adsorption performance of rGOA dependent on the reductant used for rGOAs synthesis. Efficient separation of benzene and cyclohexane has critical importance for production of commodity chemicals, and is one of the most challenging separations in the industry. Physisorption by recyclable, porous solids has a significant potential in substituting energy-intensive azeotropic or extractive distillation methods. Reduced graphene oxide aerogels (rGOAs) are emerging materials holding great promise for connecting unique properties of 2D graphene with ordinary 3D materials. The benzene/cyclohexane separation on rGOAs self-assembled by the chemical reduction with l-ascorbic acid, sodium bisulphite and (for the first time) sodium dithionite was studied by dynamic gas adsorption methods, and the adsorption performance was analysed in relation to aerogels physicochemical properties. The aerogel reduced with sodium dithionite (rGOA_DTN) had the highest reduction degree and specific surface area (461.2 m2g-1), with the highest contribution of mesopores. It was also the sample with the uppermost uptake of benzene and cyclohexane. The binary component adsorption on rGOA_DTN resulted in the selectivity of the adsorption of benzene over cyclohexane of 2.1. Adsorption-desorption studies demonstrated the excellent thermal stability of the adsorbent in the long-run operation. Because the adsorption capacity did not correlate with the mesopores but with macropores surface area, the selectivity of the adsorption was attributed to the different physicochemical structure of aerogels surface. The benzene molecule interacted strongly by specific C-H···π interactions, while the cyclohexane molecule was excluded from the surface of aerogels because of its shape/size. Results demonstrated that rGOAs can be a versatile and flexible platform for adsorptive gas-phase hydrocarbons separation.