Separation of C2H6/C2H4 mixtures is of significant importance in the chemical industry but remains a challenge due to the physicochemical similarities of C2H6 and C2H4. Herein, a metal-organic framework (MOF), [Zn4(μ4-O)(PCTF)3]n (Zn-PCTF) (PCTF2-= 5-trifluoromethyl-1H-pyrazole-4-carboxylic), is provided for the removal of C2H6 from C2H6/C2H4 mixtures. Zn-PCTF displays a three-dimensional framework featuring one-dimensional pore channels with periodic bottleneck segments. The well-balanced C2H6 adsorption capacity (79.0 cm3 g-1 at 298 K) and C2H6/C2H4 selectivity (1.8) for Zn-PCTF under ambient conditions boost Zn-PCTF with highly promising potentials for efficient purification of C2H4 from C2H6/C2H4 mixtures, which is verified by the dynamic column breakthrough experiments. The well-matched caged pores and suitable pore chemistry (particularly the presence of abundant Lewis base sites (N, O, and F) on the pore surfaces) for C2H6 account for the high-performance C2H6/C2H4 separation of Zn-PCTF unveiled by computational simulations.