The preparation of α-alumina supported zeolite Beta membranes was successfully achieved and sped up by exploring combinations of three seeding techniques and three synthetic methods. The surface of the membranes was completely covered by well intergrown crystals; the thickness of the zeolite layers ranged from 2 to 6 μm depending on the synthesis method used. The quality of the membranes was tested by means of pervaporation of ethanol/1,3,5-triisopropylbenzene (TIPB) mixtures together with permporometry experiments. The performance in the vapour separation of quaternary equimolar mixtures of n-hexane (nHEX), 3-methylpentane (3MP), 2,3-dimethylbutane (23DMB) and 2,2-dimethylbutane (22DMB) in the range 343–443 K showed that permeate flux decreases as the branching degree increases following the order: nHEX ≫ 3MP > 23DMB > 22DMB. In the retentate, the fractions of monobranched and normal hexane decrease while the concentration of dibranched isomers is increased compared to the feed composition. The influence of the temperature in the permeation fluxes indicates the existence of an activated transport mechanism which favours the permeation of more nHEX and 3MP with regard to their dibranched isomers. The octane number (ON) of the quaternary mixture was enhanced up to 5 points with the best synthesized membrane.