Industrialization and economic development have accelerated energy consumption and the release of CO2 to the atmosphere. The continual increase in CO2 levels is contributing to climate change; therefore, mitigating CO2 emissions warrants intensive research. Metal-organic frameworks (MOFs) have demonstrated potential as adsorbents for CO2 capture, but their cost makes them impractical for industrial applications. Inexpensive biomolecules, including amino acids, proteins, peptides, and porphyrins, can be used as ligands to manufacture biological MOFs (bio-MOFs) with diverse structures that can be tailored for CO2 adsorption. In this study, we discuss the application of bio-MOFs for CO2 capture. We review the principles of CO2 capture, bio-MOF CO2 adsorption chemistry, and industrial system requirements. We also review experimental and theoretical studies on bio-MOF structural parameters that affect CO2 adsorption efficiency, heat of adsorption, and selectivity. Next, we discuss the technical and economic challenges of applying bio-MOFs for CO2 capture and provide recommendations for their industrial-scale use.