An excellent performance for the kinetic separation of propene and propane is realized in two microporous MOF analogues, namely Zn(ox)0.5(trz) and Zn(ox)0.5(atrz). The great difference in diffusivity of propane and propene in Zn(ox)0.5(trz) at 323 K results in a kinetic separation factor of 1565, marking the highest value among all MOFs reported for kinetic separation of the two hydrocarbon species. The high selectivity is attributed primarily to the appropriate pore apertures.