The pore-size effect on ethane adsorption and ethane/ethylene separation in three isostructural metal azolate frameworks (MAF-123-Mn/Zn/Cu) were thoroughly investigated. MAF-123-Mn/Zn/Cu were synthesized by the solvothermal method on a gram scale. Decreasing the pore size from 6.1 to 4.9 angstrom leads to an increase in the ethane adsorption energy from 23 to 27.5 kJ mol(-1) and further ethane/ethylene separation efficiency. Molecule simulations revealed that a shorter ethane-framework interaction distance in MAF-123-Zn than that in MAF-123-Mn is responsible for the increased adsorption energy. Dynamic breakthrough experiments manifest that these metal azolate frameworks can effectively produce high-purity ethylene from ethane in one adsorption step.