The separation of ethane and ethylene is an important segment in the purification of chemical raw materials in industrial production. However, due to their similar physical and chemical properties, the separation of C 2 H 6 /C 2 H 4 is challenging.  Herein, we report the selective adsorption of ethane over ethylene by a microporous metal-organic framework with nonpolar aromatic rings constructed channels, [Co 1.5 (TATB)(H 2 O) 0.5 ]·5DMA·3H 2 O ( Co-TATB , H 3 TATB = 4,4’,4’’-(s-triazine-2,4,6-triyl) tribenzoic acid). This compound showed a higher ethane capacity than that of ethylene, and a low adsorption enthalpy of ethane only of 19.4 kJ mol −1 . Further, the dynamic breakthrough experimental confirmed that Co-TATB can selectively adsorb ethane from ethane/ethylene separation.