Separation and recovery of C2H6 and C3H8 from natural gas is a potentially economical but challenging subject in the petroleum industry. In this work, we report a stable pillared-layer microporous MOF, Ni(TMBDC)(DABCO)0.5 for the separation of C2H6 and C3H8 from natural gas. Ni(TMBDC)(DABCO)0.5 remained intact structure after exposure to humid air with RH = 100% for days. Derived from the combination of dense and accessible methyl group and methylene group in the channel, Ni(TMBDC)(DABCO)0.5 exhibited strong affinity toward C3H8 and C2H6, with remarkably high capacities of 2.80 mmol/g at 1 kPa and 3.37 mmol/g at 5 kPa for C3H8, as well as 2.93 mmol/g at 10 kPa for C2H6. Its IAST selectivities of C3H8/CH4 and C2H6/CH4 reached 274 and 29, respectively. The complete separation of CH4/C2H6/C3H8 ternary mixture on breakthrough experiment demonstrated the great potential on recovery of C2H6 and C3H8 from natural gas through a Ni(TMBDC)(DABCO)0.5 packed column.