Rising CO2 levels in the atmosphere resulting from fossil fuel combustion is one of the most significant global environmental concerns. Carbon capture and sequestration (CCS), primarily post-combustion CO2 capture, is an essential research area to reduce CO2 levels and avoid environmental destabilization. Recently, metal–organic frameworks (MOFs) have been attracting attention in the scientific community for potential applications in gas storage and separation, including CCS, owing to their novel properties, such as a large surface area, tunable pore shape and size, and tailored chemical functionality. This chapter starts with a brief introduction about the significance of CO2 adsorption and separation, followed by how MOF-based research endeavors were initiated and explored, and why MOFs are unique for gas adsorption. Secondly, we reviewed the relationship between CO2 adsorption and MOF properties including surface area, pore size and volume, amine functionality, nature of linkers, and structural flexibility, and analyzed the reported data based on the possible adsorption mechanism. The humidity effects on CO2 capture over MOFs and implementation of MOF composites were considered as well. Finally, some conclusions on the status of the developed MOFs and perspectives for future research on MOFs for the practical application of CO2 adsorption and separation were mentioned.