As a major greenhouse gas, the continuous increase of carbon dioxide (CO₂) in the atmosphere has caused serious environmental problems, although CO₂ is also an abundant, inexpensive, and nontoxic carbon source. Here, we use metal-organic framework (MOF) with highly ordered hierarchical structure as adsorbent and catalyst for chemical fixation of CO₂ at atmospheric pressure, and the CO₂ can be converted to the formate in excellent yields. Meanwhile, we have successfully integrated highly ordered macroporous and mesoporous structures into MOFs, and the macro-, meso-, and microporous structures have all been presented in one framework. Based on the unique hierarchical pores, high surface area (592 m²/g), and high CO₂ adsorption capacity (49.51 cm³/g), the ordered macroporous-mesoporous MOFs possess high activity for chemical fixation of CO₂ (yield of 77%). These results provide a promising route of chemical CO₂ fixation through MOF materials.