As an effective strategy to establish a sustainable society, reliable materials and technologies for CO₂ capture and conversion are highly required. Due to large surface area, high porosity and tunability, metal-organic frameworks (MOFs) are promising candidates for CO₂ capture and conversion. On one hand, MOFs have been widely used for CO₂ adsorption and separation owing to their cavities. On the other hand, the structures and functionality of MOFs are easily tuned, and then the catalytically active centers for CO₂ conversion can be incorporated into the framework. Our work herein is concentrated on the synthesis and application of porphyrinic metal-organic frameworks (PMOFs) in CO₂ capture and conversion. Catalytic results show that under the visible light (> 400 nm) irradiation without any additional photosensitizer, our PMOFs are powerful to catalyze CO₂ reduction to the formate ion with up to 99% selectivity and can be recycled and reused for 3 runs without significant loss of the activity. Furthermore, our PMOFs can promote the cycloaddition of CO₂ and epoxides under low CO₂ concentrations (e.g. 50%, 30%, 15% and 5%) due to the CO₂ concentrating effect from the pore spaces.