​The cobalt-based ZIF-67 has been evaluated for the adsorptive propylene/propane separation in a fixed bed. Characterization techniques and dynamic measurements have been performed over ZIF-67 to evaluate its potential in this defiant process. Cobalt promotes a more rigid framework than zinc in the isostructural ZIF-8. Although the adsorption affinity of ZIF-67 for both hydrocarbons is similar, the lower flexibility of the framework makes ZIF-67 behaving with a clear preference towards propane. This inverse selectivity promotes the enrichment in propylene content upon breakthrough, and may simplify the separation scheme. Therefore, ZIF-67 adsorptive separation is presented as an alternative to energy-demanding distillation.​