The removal of trace amounts of propyne from propylene is critical for the production of polymer-grade propylene. We herein report the first example of metal-organic frameworks of flexible-robust nature for the efficient separation of propyne/propylene mixtures. The strong binding affinity and suitable pore confinement for propyne account for its high uptake capacity and selectivity, as evidenced by neutron powder diffraction studies and density functional theory calculations. The purity of the obtained propylene is over 99.9998%, as demonstrated by experimental breakthrough curves for a 1/99 propyne/propylene mixture.