The separation of propylene and propane is an important but challenging process

primarily achieved through energy-intensive distillation technology in the petrochemical industry. Here

we reported two natural C

4

linkers based metal–organic frameworks (MIP-202 and MIP-203) for C

3

H

6

/C

3

H

8

separation. Adsorption isotherms and selectivity calculations were performed to study the adsorption performance for C

3

H

6

/C

3

H

8

separation. Results show that C

3

H

6

/C

3

H

8

uptake ratios (298 K

100 kPa) for MIP-202 and MIP-203 are 2.34 and 7.4

respectively. C

3

H

6

/C

3

H

8

uptake ratio (303 K

100 kPa) for MIP-203 is up to 50.0. The mechanism for enhanced separation performance of C

3

H

6

/C

3

H

8

on MIP-203 at higher temperature (303 K) was revealed by the

in situ

PXRD characterization. The adsorption selectivities of C

3

H

6

/C

3

H

8

on MIP-202 and MIP-203 (298 K

100 kPa) are 8.8 and 551.4

respectively. The mechanism for the preferential adsorption of

C

3

H

6

over C

3

H

8

in MIP-202 and MIP-203 was revealed by the Monte Carlo simulation. The cost of organic ligands for MIP-202 and MIP-203 was lower than that of organic ligands for those top-performance MOFs. Our work sets a new benchmark for C

3

H

6

sorbents with high adsorption selectivities.