A robust microporous aluminum tetracarboxylate framework, MIL-120(Al)-AP, is reported for post-combustion carbon capture. This material exhibits high CO₂ uptake (1.9 mmol g⁻¹ at 0.1 bar, 298 K) and favorable CO₂ capture configuration with high-density μ₂-OH groups and accessible aromatic rings. Calculations and experimental evidence suggest a moderate host-guest interaction (Qst = -40 kJ mol⁻¹), indicating a relatively low energy penalty for regeneration. An environmentally friendly ambient pressure synthesis method is developed to prepare MIL-120(Al)-AP at the kilogram scale with high yield, and the MOF is shaped into mechanically stable millimeter-sized beads. First evidence of efficient CO₂/N₂ separation is validated by breakthrough experiments, while operando IR experiments indicate favorable CO₂ adsorption over water. A techno-economic analysis estimates a production cost of ≈13 kg⁻¹, significantly lower than other benchmark MOFs. These advancements make MIL-120(Al)-AP an excellent candidate for industrial-scale CO₂ capture processes. MIL-120(Al)-AP is a robust microporous aluminum tetracarboxylate framework with high CO₂ uptake and favorable CO₂ capture configuration. It exhibits a moderate host-guest interaction (Qst = -40 kJ mol⁻¹), indicating a relatively low energy penalty for regeneration. An environmentally friendly ambient pressure synthesis method is developed to prepare MIL-120(Al)-AP at the kilogram scale with high yield, and the MOF is shaped into mechanically stable millimeter-sized beads. First evidence of efficient CO₂/N₂ separation is validated by breakthrough experiments, while operando IR experiments indicate favorable CO₂ adsorption over water. A techno-economic analysis estimates a production cost of ≈13 kg⁻¹, significantly lower than other benchmark MOFs. These advancements make MIL-120(Al)-AP an excellent candidate for industrial-scale CO₂ capture processes.A robust microporous aluminum tetracarboxylate framework, MIL-120(Al)-AP, is reported for post-combustion carbon capture. This material exhibits high CO₂ uptake (1.9 mmol g⁻¹ at 0.1 bar, 298 K) and favorable CO₂ capture configuration with high-density μ₂-OH groups and accessible aromatic rings. Calculations and experimental evidence suggest a moderate host-guest interaction (Qst = -40 kJ mol⁻¹), indicating a relatively low energy penalty for regeneration. An environmentally friendly ambient pressure synthesis method is developed to prepare MIL-120(Al)-AP at the kilogram scale with high yield, and the MOF is shaped into mechanically stable millimeter-sized beads. First evidence of efficient CO₂/N₂ separation is validated by breakthrough experiments, while operando IR experiments indicate favorable CO₂ adsorption over water. A techno-economic analysis estimates a production cost of ≈13 kg⁻¹, significantly lower than other benchmark MOFs. These advancements make MIL-120(Al)-AP an excellent candidate for industrial-scale CO₂ capture processes. MIL-120(Al)-AP is a robust microporous aluminum tetracarboxylate framework with high CO₂ uptake and favorable CO₂ capture configuration. It exhibits a moderate host-guest interaction (Qst = -40 kJ mol⁻¹), indicating a relatively low energy penalty for regeneration. An environmentally friendly ambient pressure synthesis method is developed to prepare MIL-120(Al)-AP at the kilogram scale with high yield, and the MOF is shaped into mechanically stable millimeter-sized beads. First evidence of efficient CO₂/N₂ separation is validated by breakthrough experiments, while operando IR experiments indicate favorable CO₂ adsorption over water. A techno-economic analysis estimates a production cost of ≈13 kg⁻¹, significantly lower than other benchmark MOFs. These advancements make MIL-120(Al)-AP an excellent candidate for industrial-scale CO₂ capture processes.