It is of vital importance to research carbon dioxide (CO2) removal from flue gas and natural gas. Metal-organic frameworks have been widely used in the adsorption field because of their high specific surface area, high porosity and special chemical properties. With the exception of separation performance, synthesis cost and energy consumption are also be considered in actual industry. Here, an ultra-microporous metal-organic framework CPM-20(Co) with mixed ligand was synthesized using cheap and convenient ligands (1,4-dicarboxybenzene and isonicotinic acid). The calculation shows the adsorption heat of CO2 was 20.16 kJ/mol resulting low regenerative energy. This material exhibits high selectivities of equimolar mixture CO2/N2 (350) and CO2/CH4 (45) at 298 K and 1 bar, which is better than other MOFs reported. Breakthrough experiments confirmed that CPM-20(Co) can separate CO2 from flue gas and natural gas under environmental conditions. It is speculated that the framework has suitable pore size and higher polarizability of CO2 are the key factor for CPM-20(Co) to achieve the adsorption separation of CO2/N2 and CO2/CH4. CPM-20(Co) has low regenerative energy and the material was easily obtained, which has a better application prospect in industry.