Multicomponent adsorption of alkanes in the C5-C6 range was investigated in a sample of zeoliteBETA. 6-components breakthrough experiments were performed showing interesting properties forthe separation of the light naphtha fraction. The lower adsorption enthalpy of C5 alkanes was explored by a temperature sensibility analysis demonstrating that at 583 K C5/C6 equimolar mixture can be separated in a single step into low and high octane number (RON) fractions. The separation 23DMB/3MP can not be achieved in the case of mixtures with the typical composition of the isomerization products, but zeolite BETA still selective for 22DMB resulting in a slight increase of the RON comparatively to the final isomerate from the conventional processes