Separation of hydrocarbons is one of the most energy demanding processes. The need to develop materials for the selective adsorption of hydrocarbons, under reasonable conditions, is therefore of paramount importance. This work unveils unexpected hydrocarbon selectivity in a flexible Metal–Organic Framework (MOF), based on differences in their gate opening pressure. We show selectivity dependence on both chain length and specific framework–gas interaction. By combining Raman spectroscopy and theoretical van der Waals Density Functional (vdW-DF) calculations, the separation mechanisms governing this unexpected gate-opening behavior are revealed.